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Sample records for radiation graft polymerization

  1. Process for radiation grafting hydrogels onto organic polymeric substrates

    DOEpatents

    Ratner, Buddy D.; Hoffman, Allan S.

    1976-01-01

    An improved process for radiation grafting of hydrogels onto organic polymeric substrates is provided comprising the steps of incorporating an effective amount of cupric or ferric ions in an aqueous graft solution consisting of N-vinyl-2 - pyrrolidone or mixture of N-vinyl-2 - pyrrolidone and other monomers, e.g., 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, propylene glycol acrylate, acrylamide, methacrylic acid and methacrylamide, immersing an organic polymeric substrate in the aqueous graft solution and thereafter subjecting the contacted substrate with ionizing radiation.

  2. Radiation-induced graft polymerization of amphiphilic monomers with different polymerization characteristics onto hydrophobic polysilane

    NASA Astrophysics Data System (ADS)

    Tanaka, Hidenori; Iwasaki, Isao; Kunai, Yuichiro; Sato, Nobuhiro; Matsuyama, Tomochika

    2011-08-01

    The structures of poly(methyl-n-propylsilane) (PMPrS) amphiphilically modified through γ-ray-induced graft polymerization were investigated with 1H NMR measurement. By the use of methyl methacrylate (MMA) or diethyl fumarate (DEF) as monomers for the graft polymerization, grafting yield rose with increasing total absorption dose and monomer concentrations, but decreased with increasing dose rate. This result means that grafting yield of modified PMPrS can be controlled by changing irradiation conditions. However, the number of PMMA or PDEF graft chains per PMPrS chain was estimated to be less than 1.0 by analysis of 1H NMR spectra, and this value was lower than that we had expected. To improve graft density, maleic anhydride (MAH), which is known as a non-homopolymerizable monomer in radical polymerization, was used as a monomer for grafting. As a result, high density grafting (one MAH unit for 4.2 silicon atoms) was attained. It demonstrates that the structure of γ-ray-modified polysilane strongly depends on the polymerization characteristics of grafted monomers.

  3. Antimicrobial fabric adsorbed iodine produced by radiation-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Aoki, Shoji; Fujiwara, Kunio; Sugo, Takanobu; Suzuki, Koichi

    2013-03-01

    Antimicrobial fabric was synthesized by radiation-induced graft polymerization of N-vinyl pyrrolidone onto polyolefine nonwoven fabric and subsequent adsorption of iodine. In response of the huge request for the antimicrobial material applied to face masks for swine flu in 2009, operation procedure of continuous radiation-induced graft polymerization apparatus was improved. The improved grafting production per week increased 3.8 times compared to the production by former operation procedure. Shipped antimicrobial fabric had reached 130,000 m2 from June until December, 2009.

  4. Recent achievements in the use of radiation polymerization and grafting for biomedical applications

    NASA Astrophysics Data System (ADS)

    Carenza, Mario

    Papers mainly published in the last few years on radiation processing of polymeric systems for biomedical applications carried out in different laboratories are reviewed. Radiation-induced polymerization to obtain hydrogels as carriers for immobilization of bioactive agents and for controlled release of drugs is described. Radiation modification of polymers by graft copolymerization and/or crosslinking for the same purposes is also reported. The second part of the paper deals with the work recently carried out in the author's laboratory. Radiation-induced polymerization at low temperatures to obtain matrices susceptible to entrap drugs, including peptides and proteins, is discussed. Radiation grafting of hydrophilic monomers onto relatively new inorganic polymers, i.e. polyphosphazenes, and the properties of such modified polymeric materials, together with their biocompatibility, are summarized.

  5. Graft polymerization using radiation-induced peroxides and application to textile dyeing

    NASA Astrophysics Data System (ADS)

    Enomoto, Ichiro; Katsumura, Yosuke; Kudo, Hisaaki; Soeda, Shin

    2011-02-01

    To improve the dyeing affinity of ultra high molecular weight polyethylene (UHMWPE) fiber, surface treatment by radiation-induced graft polymerization was performed. Methyl methacrylate (MMA), acrylic acid (AA) and styrene (St) were used as the monomers. The grafting yields as a function of storage time after irradiation were examined. Although the grafting yield of St after the sulfonation processing was quite low compared with those of MMA and AA, it was successfully dyed to a dark color with a cationic dye. Some acid dyes can dye the grafted fiber with AA. The acid dye is distributed to the amorphous domains of the AA grafted fiber. The dyeing concentration depended on the grafting yield, and the higher the grafting yield the darker the dye color.

  6. Radiation-induced graft polymerization of N-vinylpyrrolidone onto segmented polyurethane based on isophorone diisocyanate

    NASA Astrophysics Data System (ADS)

    Walo, Marta; Przybytniak, Grażyna; Kavaklı, Pınar Akkas; Güven, Olgun

    2013-03-01

    A segmented polyurethane (PUR) sample based on isophorone diisocyante was modified by radiation induced-graft polymerization of N-vinylpyrrolidone. Radiation grafting was carried out by the mutual irradiation method to improve hydrophilicity of the matrix surface. Different parameters affecting the grafting yield, such as effect of dose, monomer and mineral salt concentration, were investigated. It was found that degree of grafting increased with increasing total dose and monomer concentration in the presence of small amount of homopolymer suppressor. Physicochemical properties of the control and grafted PUR were studied using infrared spectroscopy (ATR-FTIR), thermogravimetric analysis, atomic force microscopy and X-ray photoelectron spectroscopy. The wettability was evaluated by contact angle measurements.

  7. Radiation-induced polymerization and grafting of β(-)pinene on silica surface

    NASA Astrophysics Data System (ADS)

    Cataldo, Franco; Ursini, Ornella; Lilla, Edo; Angelini, Giancarlo

    2008-05-01

    Poly-β-pinene (pBp) was obtained on silica surface by γ radiation-induced polymerization of β(-)pinene in presence of silica gel with a specific surface area of 300 m 2/g. Different radiation doses were employed in the range 50-332 kGy. The pBp-silica hybrid samples obtained have been characterized by FT-IR spectroscopy and the amount of pBp on silica surface has been determined both by gravimetric and TGA measurements. The fraction of pBp chemically grafted on silica surface has been determined by the extraction of the pBp-silica hybrid with boiling toluene and was found to be 10-20% of the total pBp formed on silica surface. The optical activity of pBp extracted from the hybrid was studied by polarimetric measurements and found slightly lower than the typical specific optical rotation of pBp polymerized in bulk with radiation. The thermal stability of the pBp-silica hybrid materials was studied by thermogravimetric and differential thermal analysis. The results show lower thermal stability for the pBp-silica hybrid in comparison to pure pBp. Evidently, silica catalyzes the thermal decomposition of pBp at lower temperatures. Use of the pBp-silica hybrid as stationary phase for liquid chromatography for chiral separations has been proposed.

  8. Molecular Design, Graft Polymerization and Performance Evaluation of Radiation Curable Flame Retardant Monomers Derived from Phosphorus-Nitrogen Systems

    NASA Astrophysics Data System (ADS)

    Edwards, Brian Tyndall

    The textile industry is constantly seeking new technologies to make its production more efficient, economical and environmentally friendly. An exciting new strategy to impart value-added functional finishes to textiles is the use of radiation, such as ultraviolet (UV) light, to drive the polymerization of monomers onto the surface of the substrates. These grafted polymeric layers provide the fiber or fabric with interesting new properties, such as antimicrobial behavior, water and oil repellency or flame retardancy. With the aid of a photoinitiator, UV curing can take place very rapidly and the process is waterless and uses less energy than traditional textile wet processing. With these thoughts in mind, this research explores the molecular design, synthesis, UV induced graft polymerization and performance evaluation of nine phosphorus-based flame retardant monomers for cellulosic cotton substrates. All monomers in this work were easily prepared using one-pot reactions procedures. With the assistance of Irgacure 819 photoinitiator, seven of the nine monomers were shown to simultaneously graft and polymerize onto the surface of cotton fabrics under UV radiation. JMPRTM Pro 10 software was used to explore the effect of variables, such as monomer concentration, photoinitiator concentration and UV exposure time, on the yield of the grafted polymeric layer. Burn testing of the treated fabrics in the vertical, 45° and horizontal orientations showed that all nine monomers were effective flame retardants that function via the condensed phase mechanism by encouraging the formation of nonflammable char. These burn test results were validated by thermogravimetric analysis, which demonstrated quantitatively that all nine monomers strongly promote the generation of a protective char. Finally, scanning electron microscopy was used to examine the surface morphology of the treated fabrics and visualize the grafted polymeric layer.

  9. Radiation-induced graft polymerization of chitosan onto poly(3-hydroxybutyrate).

    PubMed

    Torres, Maykel González; Muñoz, Susana Vargas; Rosales, Silvia G Solís; Carreón-Castro, Ma del Pilar; Muñoz, Rodrigo Alonso Esparza; González, Roberto Olayo; González, Miriam Rocío Estévez; Talavera, Rogelio Rodríguez

    2015-11-20

    Chitosan is among the most studied biopolymers and offers important advantages, such as biodegradability, biocompatibility and nontoxicity. In this study, this polysaccharide was grafted onto poly(3-hydroxybutyrate) using the simultaneous gamma-irradiation-initiated polymerization method. The polyester was immersed in diverse solvents, which allowed the preparation of graft copolymers with different yields and crystallinities. A successful synthesis and the estimation of the degree of crystallinity were verified by spectroscopic and calorimetric techniques. The most suitable method was found to be the thermoanalytical approach because it displayed a linear relationship between the degree of crystallinity and the increasing degree of grafting. The results also indicated that the lowest degree of grafting was seen for acetic acid (14.27%), while the highest degree corresponded to ethyl acetate (32.11%). The mechanism of grafting was proposed on the basis of the experimental results. PMID:26344305

  10. Desalination by electrodialysis with the ion-exchange membrane prepared by radiation-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Choi, Seong-Ho; Han Jeong, Young; Jeong Ryoo, Jae; Lee, Kwang-Pill

    2001-01-01

    Ion-exchange membranes modified with the triethylamine [-N(CH 2CH 3) 3] and phosphoric acid (-PO 3 H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto the polyolefin nonwavon fabric (PNF) and subsequent chemical modification of poly(GMA) graft chains. The physical and chemical properties of the GMA-grafted PNF and the PNF modified with ion-exchange groups were investigated by SEM, XPS, TGA, and DSC. Furthermore, electrochemical properties such as specific electric resistance, transport number of K +, and desalination were examined. The grafting yield increased with increasing reaction time and reaction temperature. The maximum grafting yield was obtained with 40% (vol.%) monomer concentration in dioxane at 60°C. The content of the cation- and anion-exchange group increased with increasing grafting yield. Electrical resistance of the PNF modified with TEA and -PO 3 H group decreased, while the water uptake (%) increased with increasing ion-exchange group capacities. Transport number of the PNF modified with ion-exchange group were the range of ca. 0.82-0.92. The graft-type ion-exchange membranes prepared by radiation-induced graft copolymerization were successfully applied as separators for electrodialysis.

  11. Graft copolymers of polyurethane with various vinyl monomers via radiation-induced miniemulsion polymerization: Influential factors to grafting efficiency and particle morphology

    NASA Astrophysics Data System (ADS)

    Wang, Hua; Wang, Mozhen; Ge, Xuewu

    2009-02-01

    Graft copolymers of polyurethane (PU) with various vinyl monomers were synthesized through a one-pot but two-step miniemulsion polymerization process. Firstly, the polycondensation of isophorone diisocyanate (IPDI) with hydroxyl-terminated polybutadiene (HTPB) had been performed in aqueous miniemulsion at 40 °C in order to obtain PU dispersions. Consecutively, an in-situ graft copolymerization of the vinyl monomers with the synthesized PU was initiated by γ-ray radiation at room temperature. The grafting efficiency of PU with vinyl monomer ( GPU/monomer) was calculated from 1H NMR spectra and the particle morphology of the final hybrid latex was observed by transmission electron microscopy (TEM). As there was no monomer transferring in miniemulsion system, homogenous hybrid particles would be synthesized provided that the monomer was miscible with PU, such as styrene. With the increase of the polarity of the monomer, the compatibility of PU with monomer decreased. GPU/monomer varied as GPU/styrene(37%)> GPU/butyl acrylate (BA)(21%)> GPU/methyl methacrylate (MMA)(12%). The proportion of homogeneous nucleation would increase as the hydrophilicity of the monomer increased. High temperature would destabilize the miniemulsion so as to result in a less grafting efficiency. Compared to the phase separation during the seeded emulsion polymerization, the miniemulsion polymerization method facilitated the preparation of homogeneous materials owing to its monomer droplet nucleation mechanism.

  12. Chemical reactive filter paper prepared by radiation-induced graft polymerizationI

    NASA Astrophysics Data System (ADS)

    Dessouki, A. M.; El-Tahawy, M.; El-Boohy, H.; El-Mongy, S. A.; Badawy, S. M.

    1999-06-01

    Chelating filter papers with chemically bonded amidoxime groups were synthesized by radiation-induced grafting of acrylonitrile onto filter paper (W3) followed by chemical treatment with hydroxylamine. The effect of grafting conditions such as absorbed dose, dose rate, monomer concentration and filter paper thickness on the grafting yield was studied. It was found that the degree of grafting increases with increasing absorbed dose and dose rate, and then tends to level off at high doses. The order of the dependence of the initial grafting rate on the dose is found to be of 0.33. An increasing monomer concentration was accompanied by a significant increase in grafting. At high monomer concentration the initial rate of grafting is fast followed by a slow rate. The rate of grafting is controlled by the filter paper thickness and the diffusion of monomer into the interior of the filter paper. Mechanical properties of the prepared filter paper were improved over the ungrafted paper. The amidoxime filter papers were examined for adsorption of uranium concentration ranging between 10-100 ppm.

  13. Radiation-induced graft polymerization of acrylamide: Reverse osmosis properties of polyethylene-g-poly(acrylamide) membrane

    NASA Astrophysics Data System (ADS)

    Dessouki, Ahmed M.; Hegazy, El-Sayed A.; El-Assy, Nasef B.; El-Boohy, Hussein A.

    A study has been made of some properties of the graft copolymer obtained by direct radiation grafting of acrylamide (AAm) onto low density polyethylene (LDPE) films. The swelling behaviour was investigated for the grafted and alkali-treated graft copolymer and it was found that this depends mainly on the amount of hydrophilic groups and also on the type of electrolytes (K- or Nasalts). salts). Some other properties of the graft copolymer films such as dimensional change wet and dry, electrical conductivity, and mechanical properties were studied. A trial has been made of such membrane for reverse osmosis desalination of saline water. The effect of operating time, degree of grafting, applied pressure and feed concentration on the water flux and salt rejection was determined.

  14. The synthesis of a new type adsorbent for the removal of toxic gas by radiation-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Okamoto, Jiro; Sugo, Takanobu; Fujiwara, Kunio; Sekiguchi, Hideaki

    A new type of adsorbent containing sulfulic acid group for the removal of ammonia gas was synthesized by radiation-induced graft polymerization of styrene onto fibrous and nonwoven type polypropylene followed by sulufonation with chlorosulfonic acid. The rate of the adsorption of ammonia gas by H-type adsorbent is independent of the ion-exchange capacity. The amount of ammonia gas adsorbed by the chemical adsorption was dependent on the ion-exchange capacity of H-type fibrous adsorbent and was kept constant value in spite of the equilibrium pressure of ammonia gas. Cu(II)- and Ni(II)-types fibrous adsorbent were prepared by the ion exchange reaction of Na-type fibrous adsorbent with metal nitrate solutions. Although, the rate of adsorption of ammonia gas by metal-type fibrous adsorbent is lower than that of H-type adsorbent, the amount of ammonia gas adsorbed increase compared to H-type adsorbent with the same ion exchange capacity. It was related to the highest coordination number of metal ion. The ratio of the number of ammonia molecules adsorbed chemically and the number of metal ion adsorbed in fibrous adsorbent was 4 for Cu-type and 6 for Ni-type fibrous adsorbent, respectivelly.

  15. Simultaneous radiation induced graft polymerization of N-vinyl-2-pyrrolidone onto polypropylene non-woven fabric for improvement of blood compatibility

    NASA Astrophysics Data System (ADS)

    Li, Rong; Wang, Hengdong; Wang, Wenfeng; Ye, Yin

    2013-07-01

    In this study, N-vinyl-2-pyrrolidone (NVP) was grafted onto polypropylene non-woven fabric (PPNWF) through a simultaneous irradiation induced graft polymerization technique. Effect of the parameters of graft polymerization, i.e., monomer concentration, absorbed dose and dose rate, on the degree of grafting (DG) was investigated. The graft polymerization of NVP was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). A contact angle goniometry was used to test water contact angle (WCA) of original PPNWF and modified samples. The in vitro blood compatibility, including hemolysis, protein adsorption, platelet adhesion and activated partial thromboplastin time (APTT) of tested specimens, was evaluated. The results demonstrated that the hemocompatibility of PPNWF was improved via graft polymerization of NVP.

  16. One-step functionalization of multi-walled carbon nanotubes by radiation-induced graft polymerization and their application as enzyme-free biosensors

    NASA Astrophysics Data System (ADS)

    Yang, Dae-Soo; Jung, Da-Jung; Choi, Seong-Ho

    2010-04-01

    This paper describes the functionalization of multi-walled carbon nanotubes (MWNTs) by radiation-induced graft polymerization (RIGP) of vinyl monomers with functional groups and the application of these MWNTs in enzyme-free biosensors. The vinyl monomers used were acrylic acid (AAc), methacrylic acid (MAc), glycidyl methacrylate (GMA), maleic anhydride (MAn), and 4-vinylphenylboronic acid (VPBAc). Tubular-type MWNTs were obtained via RIGP of various vinyl monomers. The poly(VPBAc)-grafted MWNTs (PVBAc- g-MWNTs) were used as sensing sites in enzyme-free glucose sensors for the detection of glucose without enzymes. The PVBAc- g-MWNTs electrode displayed an excellent linear response to glucose concentration in the range 1.0-10 mM. The functionalized MWNTs prepared by RIGP can be used as biosensor materials.

  17. Functionalisation of PAA radiation grafted PVDF

    NASA Astrophysics Data System (ADS)

    Betz, N.; Begue, J.; Goncalves, M.; Gionnet, K.; Déléris, G.; Le Moël, A.

    2003-08-01

    The covalent bonding of amino-terminated molecules was performed onto acrylic acid radiation induced grafting poly(vinylidene fluoride) (PVDF). The polymer was irradiated with different ionizing radiation: swift heavy ions or electrons. The polymerization of acrylic acid was then performed to confer to PVDF carboxyl groups suitable for condensation with the amino groups of the other molecule. Acrylic acid swelling of PVDF films was investigated as a function of temperature and monomer concentration in order to anticipate the best grafting conditions. Grafted and functionalized films were characterized using infrared spectroscopy (transmission and ATR), and weighing measurements. The PVDF-g-PAA films exhibit different structures depending on the monomer concentration. Immobilization of an amino-terminated molecule and a peptide onto PVDF was achieved using water soluble carbodiimide.

  18. Modification of microcrystalline cellulose by gamma radiation-induced grafting

    NASA Astrophysics Data System (ADS)

    Madrid, Jordan F.; Abad, Lucille V.

    2015-10-01

    Modified microcrystalline cellulose (MCC) was prepared through gamma radiation-induced graft polymerization of glycidyl methacrylate (GMA). Simultaneous grafting was employed wherein MCC with GMA in methanol was irradiated with gamma radiation in nitrogen atmosphere. The effects of different experimental factors such as monomer concentration, type of solvent and absorbed dose on the degree of grafting, Dg, were studied. The amount of grafted GMA, expressed as Dg, was determined gravimetrically. Information from grafted samples subjected to Fourier transformed infrared spectroscopy (FTIR) in attenuated total reflectance (ATR) mode showed peaks corresponding to GMA which indicates successful grafting. The X-ray diffraction (XRD) analysis revealed that the crystalline region of MCC was not adversely affected after grafting with GMA. The thermogravimetric analysis (TGA) data showed that the decomposition of grafted MCC occurred at higher temperature compared to the base MCC polymer.

  19. Synthesis of Polymer Grafted Magnetite Nanoparticle with the Highest Grafting Density via Controlled Radical Polymerization

    NASA Astrophysics Data System (ADS)

    Babu, Kothandapani; Dhamodharan, Raghavachari

    2009-09-01

    The surface-initiated ATRP of benzyl methacrylate, methyl methacrylate, and styrene from magnetite nanoparticle is investigated, without the use of sacrificial (free) initiator in solution. It is observed that the grafting density obtained is related to the polymerization kinetics, being higher for faster polymerizing monomer. The grafting density was found to be nearly 2 chains/nm2 for the rapidly polymerizing benzyl methacrylate. In contrast, for the less rapidly polymerizing styrene, the grafting density was found to be nearly 0.7 chain/nm2. It is hypothesized that this could be due to the relative rates of surface-initiated polymerization versus conformational mobility of polymer chains anchored by one end to the surface. An amphiphilic diblock polymer based on 2-hydroxylethyl methacrylate is synthesized from the polystyrene monolayer. The homopolymer and block copolymer grafted MNs form stable dispersions in various solvents. In order to evaluate molecular weight of the polymer that was grafted on to the surface of the nanoparticles, it was degrafted suitably and subjected to gel permeation chromatography analysis. Thermogravimetric analysis, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to confirm the grafting reaction.

  20. Stepped gradients on polymeric monolithic columns by photoinitiated grafting.

    PubMed

    Currivan, Sinéad; Connolly, Damian; Paull, Brett

    2015-11-01

    The surface of polymethacrylate monoliths was functionalized by a post-polymerization modification, by means of a novel photo-initiated graft procedure where the charged monomer, sulfopropyl methacrylate, was controllably grafted stepwise, i.e. with incremental graft energies. The grafting approach was optimized using scanning capacitively coupled contactless conductivity detection. The effect of the localized ion exchange capacity and resultant gradient stationary phase upon ion-exchange chromatographic retention, selectivity, and performance was investigated, and compared to a homogeneously grafted (isotropic) column. The gradient column provided reduced peak widths at half height for both cationic analytes, with a reduction of 34 and 33%, respectively, when compared to the isotropic column. PMID:26311291

  1. Impact of solvent selection on graft polymerization of acrylamide onto starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The impact on polymer properties [molecular weight, monomer conversion, graft content, graft efficiency and anhydroglucose units between grafts (AGU/graft)] that result from changing the solvent for the graft co-polymerization of acrylamide onto starch from water to dimethylsulfoxide (DMSO) was eval...

  2. Gamma radiation grafted polymers for immobilization of Brucella antigen in diagnostic test studies

    NASA Astrophysics Data System (ADS)

    Docters, E. H.; Smolko, E. E.; Suarez, C. E.

    The radiation grafting process has a wide field of industrial applications, and in the recent years the immobilization of biocomponents in grafted polymeric materials obtained by means of ionizing radiations is a new and important contribution to biotechnology. In the present work, gamma preirradiation grafting method was employed to produce acrylics hydrogels onto polyethylene (PE), polyvinyl chloride (PVC) and polystyrene (PS). Two monomers were used to graft the previously mentioned polymers: methacrylic acid (MAAc) and acrylamide (AAm), and several working conditions were considered as influencing the degree of grafting. All this grafted polymers were used to study the possibility of a subsequent immobilization of Brucella antigen (BAg) in diagnostic test studies (ELISA).

  3. Durable Nanolayer Graft Polymerization of Functional Finishes Using Atmospheric Plasma

    NASA Astrophysics Data System (ADS)

    Mazloumpour, Maryam

    Various applications of atmospheric pressure plasma were investigated in conjunction with different chemistries on nonwoven materials including spunbond polyester (PET) and spunbod polypropylene for fuel separation and antimicrobial functionalities. Hydrophobic/Oleophobic properties were conferred on nonwoven polyester (PET) via plasma-induced graft polymerization of different hydrophobic non-C8 perfluorocarbon chemistry including perfluorohexylethylmethacrylate, perfluorohexylethylacrylate, allylpentafluorobenzene, pentafluorostyrene, or 1,3-divinyltetramethyldisiloxane in the vapor form using both in-situ and down-stream plasma configurations. Different nanolayers of the grafted polymer were furnished on nonwovens to generate surfaces with different level of wettabilities for medical applications and water/fuel separation. The effect of various hydrophobic chemistry, different plasma conditions, and plasma device parameters including plasma power and plasma exposure time were studied and the performance was characterized by measuring the contact angle and the wettability rating against liquids with broad range of surface tensions. Vapor deposition of 2-(perfluorohexyl)ethyl methacrylate and pentafluorostyrene on nonwoven PET followed by plasma-induced graft polymerization was investigated for possible use in water/fuel separation. Different nanolayer thicknesses (80-180nm) of the grafted polymer were achieved to generate surfaces with different wettabilities for water/fuel separation of different fuel compositions. The effect of different plasma conditions and device parameters including the flow rate of monomers, power of the device, and time of plasma exposure on the separation of different fuels was studied and characterized by measuring the surface energy of the treated substrates. The surface chemistry and morphology of the treated samples were characterized using XPS, SEM and TOF-SIMS techniques which confirmed the grafting of monomer onto the substrate. Furthermore, spunbond nonwoven polypropylene fabric, commonly used for hygienic products, was treated with diallyldimethylammonium chloride (DADMAC). Atmospheric pressure glow discharge plasma was used to induce free radical chain polymerization of the ADMAC monomer, which conferred a graft polymerized network on the fabric with durable antimicrobial properties. The effect of different DADMAC concentration, and plasma conditions including the RF power and the time of plasma exposure were studied and the optimum treatment conditions were identified by calculating the surface charge density on the treated fabrics. The presence of poly-DADMAC on the polypropylene surface was confirmed using SEM, FT-IR and TOF-SIMS. Antibacterial performance was investigated using standard test methods (AATCC TM 100) for both gram positive and gram negative bacteria. The antimicrobial results showed 6 log reductions in the bacterial activities of K. pneumoniae and S .aureus, which was unprecedented using a plasma-induced graft polymerization approach.

  4. Preparation of a Proton-Exchange Me mbrane with -SO3H Group Based on Polyethylene and Poly(vinylidene fluoride) Film by Radiation-Induced Graft Polymerization for Proton-Exchange Fuel Cell.

    PubMed

    Kim, Sang-Kyum; Lee, Yong-Sang; Koo, Kee-Kahb; Kim, Sang-Ho; Choi, Seong-Ho

    2015-09-01

    This paper reports the preparation of a proton-exchange membrane (PEM) with sulfonic acid (-SO3H) groups based on polyethylene (PE) films and poly(vinylidene fluoride) (PVdF) films by the radiation-induced graft polymerization (RIGP) of sodium styrene sulfonate (NaSS) in the presence of the polymerizable access agents, such as acrylic acid and pyrollidone in a methanol solution. A PEM with -SO3H based on PE and PVdF films were confirmed by ATR, XPS and contact angle measurements. The water uptake (%), graft yield (%), ion-exchange content (mmol/g), and proton conductivity (S/cm), as well as the current density (mA/cm2), and power density (mW/cm) for PEM with -SO3H groups prepared by RIGP were evaluated. The PEM prepared with the -SO3H groups based on PE and PVdF films can be used as a proton-exchange fuel cell membrane. PMID:26716266

  5. Radiation-hardened polymeric films

    DOEpatents

    Arnold, C. Jr.; Hughes, R.C.; Kepler, R.G.; Kurtz, S.R.

    1984-07-16

    The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10/sup 15/ to 10/sup 21/ molecules of dopant/cm/sup 3/. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

  6. Radiation-hardened polymeric films

    DOEpatents

    Arnold, Jr., Charles; Hughes, Robert C.; Kepler, R. Glen; Kurtz, Steven R.

    1986-01-01

    The radiation-induced conductivity of polymeric dielectrics with low electronic mobility is reduced by doping with electron donor or electron acceptor compounds at a level of 10.sup.15 to 10.sup.21 molecules of dopant/cm.sup.3. Polyesters, polyolefins, perfluoropolyolefins, vinyl polymers, vinylidene polymers, polycarbonates, polysulfones and polyimides can benefit from such a treatment. Usable dopants include 2,4,7-trinitro-9-fluorenone, tetracyanethylene, 7,7,8,8-tetracyanoquinodimethane, m-dinitrobenzene, 2-isopropylcarbazole, and triphenylamine.

  7. Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

    SciTech Connect

    Tang, Mingyi; Xu, Xiaoyang; Wu, Tao; Zhang, Sai; Li, Xianxian; Li, Yi

    2014-12-15

    Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.

  8. GRAFT POLYMERIZATION OF ACRYLONITRILE ONTO STARCH-COATED POLYETHYLENE FILM SURFACES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    When starch-coated polyethylene (PE) films were allowed to react with acrylonitrile in the presence of ceric ammonium nitrate initiator, graft polymerization occurred to produce starch-polyacrylonitrile (PAN) coatings that contained about 25% grafted PAN, by weight. The graft copolymer coatings adh...

  9. Radiation grafting of methyl methacrylate monomer on natural rubber latex. [Gamma radiation

    SciTech Connect

    Sundardi, F.; Kadariah, S.

    1984-05-01

    A method of radiation grafting of methyl methacrylate (MMA) monomer on natural rubber (NR) latex has been studied. The irradiation dose in radiation emulsion polymerization of MMA monomer was lower compared to the irradiation dose for grafting of MMA monomer on NR latex, in order to obtain the same degree of conversion. This is due to the size of the rubber particles which are quite large and, hence, not sufficient to ensure an ideal emulsion polymerization. The irradiation dose for radiation grafting of MMA monomer on latex was around 300 krad to obtain a 75% degree of conversion. However, this irradiation dose was lower compared to the irradiation dose for bulk polymerization of MMA momomer, in order to obtain the same degree of conversion. This is due to the gel effect in the viscous media. Radiation grafting of MMA monomer on NR latex does not influence the pH of the latex, but influences the viscosity significantly. The viscosity of the NR latex increased with an increase in irradiation dose, due to the increase of the total solid content in the latex. The MMA monomer converted to P-MMA in NR latex was largely grafted on the NR, or at least insoluble in a solvent for P-MMA, such as acetone or toluene. The hardness of the pure gum vulcanizate increased with an increase in the degree of grafting or P-MMA content, but the other physical properties, such as tensile strength, modulus, elongation at break, and thermal stability, were not greatly influenced by the degree of grafting. 9 references, 3 figures, 5 tables.

  10. Radiation grafting on natural films

    NASA Astrophysics Data System (ADS)

    Lacroix, M.; Khan, R.; Senna, M.; Sharmin, N.; Salmieri, S.; Safrany, A.

    2014-01-01

    Different methods of polymer grafting using gamma irradiation are reported in the present study for the preparation of newly functionalized biodegradable films, and some important properties related to their mechanical and barrier properties are described. Biodegradable films composed of zein and poly(vinyl alcohol) (PVA) were gamma-irradiated in presence of different ratios of acrylic acid (AAc) monomer for compatibilization purpose. Resulting grafted films (zein/PVA-g-AAc) had their puncture strength (PS=37-40 N mm-1) and puncture deformation (PD=6.5-9.8 mm) improved for 30% and 50% PVA in blend, with 5% AAc under 20 kGy. Methylcellulose (MC)-based films were irradiated in the presence of 2-hydroxyethyl methacrylate (HEMA) or silane, in order to determine the effect of monomer grafting on the mechanical properties of films. It was found that grafted films (MC-g-HEMA and MC-g-silane) using 35% monomer performed higher mechanical properties with PS values of 282-296 N mm-1 and PD of 5.0-5.5 mm under 10 kGy. Compatibilized polycaprolactone (PCL)/chitosan composites were developed via grafting silane in chitosan films. Resulting trilayer grafted composite film (PCL/chitosan-g-silane/PCL) presented superior tensile strength (TS=22 MPa) via possible improvement of interfacial adhesion (PCL/chitosan) when using 25% silane under 10 kGy. Finally, MC-based films containing crystalline nanocellulose (CNC) as a filling agent were prepared and irradiated in presence of trimethylolpropane trimethacrylate (TMPTMA) as a grafted plasticizer. Grafted films (MC-g-TMPTMA) presented superior mechanical properties with a TS of 47.9 MPa and a tensile modulus (TM) of 1792 MPa, possibly due to high yield formation of radicals to promote TMPTMA grafting during irradiation. The addition of CNC led to an additional improvement of the barrier properties, with a significant 25% reduction of water vapor permeability (WVP) of grafted films.

  11. Thermal stability of grafted fibers. [Gamma radiation

    SciTech Connect

    Sundardi, F.; Kadariah; Marlianti, I.

    1983-10-01

    Presented the experimental results on the study of thermal stability of grafted fibers, i.e., polypropylene-, polyester-, and rayon-grafted fibers. These fibers were obtained by radiation grafting processes using hydrophylic monomers such as 1-vinyl 2-pyrolidone, acrylic acid, N-methylol acrylamide, and acrylonitrile. The thermal stability of the fibers was studied using a Shimadzu Thermal Analyzer DT-30. The thermal stability of the fibers, which can be indicated by the value of the activation energy for thermal degradation, was not improved by radiation grafting. The degree of improvement depends on the thermal stability of the monomers used for grafting. The thermal stability of a polypropylene fiber, either a grafted or an ungrafted one, was found to be inferior compared to the polyester of a rayon fiber, which may be due to the lack of C=O and C=C bonds in the polypropylene molecules. The thermal stability of a fiber grafted with acrylonitrile monomer was found to be better than that of an ungrafted one. However, no improvement was detected in the fibers grafted with 1-vinyl 2-pyrrolidone monomer, which may be due to the lower thermal stability of poly(1-vinyl-2-pyrrolidone), compared to the polypropylene or polyester fibers. 17 figures, 3 tables.

  12. Surface modification of ultra high molecular weight polyethylene fibers via the sequential photoinduced graft polymerization

    NASA Astrophysics Data System (ADS)

    Li, Zhi; Zhang, Wei; Wang, Xinwei; Mai, Yongyi; Zhang, Yumei

    2011-06-01

    In this study, a sequential photoinduced graft polymerization process was proposed to improve the poor interfacial bonding property of ultra high molecular weight polyethylene (UHMWPE) fibers. The polymerization was initiated by dormant semipinacol (SP) groups and carried out in a thin liquid layer. Methacrylic acid (MAA) and acryl amide (AM) were grafted stepwise onto the surface of UHMWPE fibers. Attenuated total reflectance infrared spectroscopy (ATR-IR) and thermo gravimetric analysis (TGA) confirmed the grafting. The analysis result of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) indicated the structure of grafted chains. Scanning electron microscopy (SEM) images and atomic force microscopy (AFM) images revealed the apparent morphology changing, and the grafted layers were observed. Interfacial shear stress (IFSS) test of the modified fibers showed an extensively improved interfacial bonding property. The active groups grafted onto the fibers would supply enough anchor points for the chemical bonding with various resins or further reactions.

  13. Synthesis of antibacterial cotton fabric by radiation-induced grafting of [2-(Methacryloyloxy)ethyl]trimethylammonium chloride (MAETC) onto cotton

    NASA Astrophysics Data System (ADS)

    Goel, N. K.; Rao, M. S.; Kumar, Virendra; Bhardwaj, Y. K.; Chaudhari, C. V.; Dubey, K. A.; Sabharwal, S.

    2009-06-01

    Gamma radiation has been used to covalently link polymer chains of [2-(Methacryloyloxy)ethyl]trimethylammonium chloride (MAETC) to cotton fabric by mutual radiation grafting. The grafted samples have been characterized for water uptake, surface morphology and thermal stability. Grafting extent was found to increase with the dose and monomer concentration. However high dose rate, O 2, inorganic salts and alcohols suppressed grafting. Radiation polymerized poly(MAETC) and MAETC-g-cotton samples were tested for their antibacterial efficacy against various bacteria and were found to possess significant antibacterial activity.

  14. Study and Optimization on graft polymerization under normal pressure and air atmospheric conditions, and its application to metal adsorbent

    NASA Astrophysics Data System (ADS)

    Ueki, Yuji; Chandra Dafader, Nirmal; Hoshina, Hiroyuki; Seko, Noriaki; Tamada, Masao

    2012-07-01

    Radiation-induced graft polymerization of glycidyl methacrylate (GMA) onto non-woven polyethylene (NWPE) fabric was achieved under normal pressure and air atmospheric conditions, without using unique apparatus such as glass ampoules or vacuum lines. To attain graft polymerization under normal pressure and air atmospheric conditions, the effects of the pre-irradiation dose, pre-irradiation atmosphere, pre-irradiation temperature, de-aeration of GMA-emulsion, grafting atmosphere in a reactor, and dissolved oxygen (DO) concentration in GMA-emulsion on the degree of grafting (Dg) were investigated in detail. It was found that the DO concentration had the strongest influence, the pre-irradiation dose, de-aeration of emulsion and grafting atmosphere had a relatively strong impact, and the pre-irradiation atmosphere and pre-irradiation temperature had the least effect on Dg. The optimum DO concentration before grafting was 2.0 mg/L or less. When a polyethylene bottle was used as a reactor instead of a glass ampoule, graft polymerization under normal pressure and air atmospheric conditions could be achieved under the following conditions; the pre-irradiation dose was more than 50 kGy, the volume ratio of GMA-emulsion to air was 50:1 or less, and the DO concentration in GMA-emulsion during grafting was below 2.0 mg/L. Under these grafting conditions, Dg was controlled within a range of up to 362%. The prepared GMA-grafted NWPE (GMA-g-NWPE) fabric was modified with a phosphoric acid to obtain an adsorbent for heavy metal ions. In the column-mode adsorption tests of Pb(II), the adsorption performance of the produced phosphorylated GMA-g-NWPE fabric (fibrous metal adsorbent) was not essentially dependent on the flow rate of the feed. The breakthrough points of 200, 500, and 1000 h-1 in space velocity were 483, 477 and 462 bed volumes, and the breakthrough capacities of the three flow rates were 1.16, 1.15 and 1.16 mmol-Pb(II)/g-adsorbent.

  15. The synthesis of well-defined poly(vinylbenzyl chloride)-grafted nanoparticles via RAFT polymerization.

    PubMed

    Moraes, John; Ohno, Kohji; Gody, Guillaume; Maschmeyer, Thomas; Perrier, Sébastien

    2013-01-01

    We describe the use of one of the most advanced radical polymerization techniques, the reversible addition fragmentation chain transfer (RAFT) process, to produce highly functional core-shell particles based on a silica core and a shell made of functional polymeric chains with very well controlled structure. The versatility of RAFT polymerization is illustrated by the control of the polymerization of vinylbenzyl chloride (VBC), a highly functional monomer, with the aim of designing silica core-poly(VBC) shell nanoparticles. Optimal conditions for the control of VBC polymerization by RAFT are first established, followed by the use of the "grafting from" method to yield polymeric brushes that form a well-defined shell surrounding the silica core. We obtain particles that are monodisperse in size, and we demonstrate that the exceptional control over their dimensions is achieved by careful tailoring the conditions of the radical polymerization. PMID:23843918

  16. 3D-Printed Biodegradable Polymeric Vascular Grafts.

    PubMed

    Melchiorri, Anthony J; Hibino, Narutoshi; Best, C A; Yi, T; Lee, Y U; Kraynak, C A; Kimerer, Lucas K; Krieger, A; Kim, P; Breuer, Christopher K; Fisher, John P

    2016-02-01

    Congenital heart defect interventions may benefit from the fabrication of patient-specific vascular grafts because of the wide array of anatomies present in children with cardiovascular defects. 3D printing is used to establish a platform for the production of custom vascular grafts, which are biodegradable, mechanically compatible with vascular tissues, and support neotissue formation and growth. PMID:26627057

  17. Comparison of surface modifications of poly(ether urethanes) by chemical infusion and graft polymerization

    SciTech Connect

    Wrobleski, D.A.; Cash, D.L.; Hermes, R.E.

    1988-01-01

    Our approach to surface modification uses the chemical infusion process to introduce materials into the outermost layer of the polymeric material, thereby altering the surface without changing the bulk properties of the polymer. The infused materials may slowly diffuse out of the infusion layer if they are volatile or highly mobile. However, if polymeric infusant materials are employed, they may become chain entangled with the host polymer and result in a permanently modified surface. A second approach utilizes photo-initiated graft polymerization of poly(ether urethanes) with an appropriate monomer. We have explored both of these methods by examining the infusion of polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG) into commercially available poly(ether urethanes) and the graft polymerization of N-vinyl pyrrolidone onto poly(ether urethanes). Results are presented here. 7 refs., 1 tab.

  18. The Synthesis of Cellulose Graft Copolymers Using Cu(0)-Mediated Polymerization

    NASA Astrophysics Data System (ADS)

    Donaldson, Jason L.

    Cellulose is the most abundant renewable polymer on the planet and there is great interest in expanding its use beyond its traditional applications. However, its hydrophilicity and insolubility in most common solvent systems are obstacles to its widespread use in advanced materials. One way to counteract this is to attach hydrophobic polymer chains to cellulose: this allows the properties of the copolymer to be tailored by the molecular weight, density, and physical properties of the grafts. Two methods were used here to synthesize the graft copolymers: a 'grafting-from' approach, where synthetic chains were grown outward from bromoester moieties on cellulose (Cell-BiB) via Cu(0)-mediated polymerization; and a 'grafting-to' approach, where fully formed synthetic chains with terminal sulfide functionality were added to cellulose acetate with methacrylate functionality (CA-MAA) via thiol-ene Michael addition. The Cell-BiB was synthesized in the ionic liquid 1-butyl-3-methylimidazolium chloride and had a degree of substitution of 1.13. Polymerization from Cell-BiB proceeded at similar but slightly slower rate than an analogous non-polymeric initiator (EBiB). The average graft density of poly(methyl acrylate) chains was 0.71 chains/ring, with a maximum of 1.0 obtained. The graft density when grafting poly(methyl methacrylate) was only 0.15, and this appeared to be due to the slow initiation of BiB groups. Using EBiB to model the reaction and improve the design should allow this to be overcome. Chain extension experiments demonstrated the living behaviour of the polymer. The CA-MAA was synthesized by esterification with methacrylic acid. Reactions of CA-MAA with thiophenol and dodecanethiol resulted in quantitative addition of the thiol to the alkene. The grafts were synthesized by Cu(0)-mediated polymerization from a bifunctional initiator containing a disulfide bond, followed by reduction to sulfides. The synthetic polymers were successfully grafted to CA-MAA but the grafting yield was limited by the low sulfide functionality. Better retention of sulfide functionality is necessary for more efficient grafting.

  19. Modification of polymeric substrates using surface-grafted nanoscaffolds

    NASA Astrophysics Data System (ADS)

    Thompson, Kimberlee Fay

    Surface grafting and modification of poly(acrylic acid) (PAA) were performed on nylon 6,6 carpet fibers to achieve permanent stain and soil resistance. PAA was grafted to nylon and modified with 1H, 1H-pentadecafluorooctyl amine (PDFOA) using an amidation agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM). The first goal was to optimize acrylamide modification of PAA in solution. Aqueous reactions with taurine, hydroxyethyl amine, and butyl amine progressed ˜100%, while PDFOA reactions in MeOH progressed ˜80%. Reaction products precipitated at 77% butyl or 52% PDFOA acrylamide contents. The second goal was to optimize the PAA grafting process. First, PAA was adsorbed onto nylon 6,6 films. Next, DMTMM initiated grafting of adsorbed PAA. PAA surface coverage was ˜78%, determined by contact angle analysis of the top 0.1--1 nm and x-ray photoelectron spectroscopy (XPS) analysis of the top 3--10 nm. The third goal was to modify PAA grafted nylon films with butyl amine and PDFOA. Randomly methylated beta-cyclodextrin (RAMEB) solubilized PDFOA in water. Contact angle detected ˜100% surface reaction for each amine, while XPS detected ˜77% butyl amine (H2O) and ˜50% for PDFOA (MeOH or H2O pH = 7) reactions. In H2O pH = 12, the PDFOA reaction progressed ˜89%, perhaps due to greater efficiency, access and solubility. The fourth goal was to perform surface depth profiling via angle-resolved XPS analysis (ARXPS). The PAA surface coverage from contact angle and XPS was confirmed. Further, adsorbed PAA was thicker than grafted PAA, supporting the theory that PAA adsorption occurs in thick layers onto nylon followed by DMTMM-activated spreading and grafting of thinner PAA layers across the surface. The PDFOA reaction in McOH produced a highly fluorinated but thin exterior and an unreacted PAA interior. The PDFOA reaction in H 2O pH = 12 produced a completely fluorinated exterior and highly fluorinated interior. Thus surface modification levels from contact angle and XPS were confirmed. The final goal was to PAA-graft and PDFOA-modify nylon 6,6 fabrics and carpets. PDFOA modification achieved significant water and oil repellency. Stainblocking was slightly improved for ionized PAA-g-nylon and greatly improved for PDFOA-modified PAA-g-nylon. However, traditional stainblockers may be necessary to completely prevent dye penetration into carpet tufts.

  20. Technique of radiation polymerization in fine art conservation: a potentially new method of restoration and preservation. [Uv and electron beams

    SciTech Connect

    Garnett, J.L.; Major, G.

    1982-01-01

    The technique of using radiation polymerization for the restoration and preservation of art treasures is considered. The processes discussed include both radiation grafting and rapid cure procedures, particularly reactions initiated by uv and eb. Representative examples where the technique has already been used are treated including typical applications with paintings, tapestries, leather and archival repair. The structure of the monomers and oligomers used in both grafting and rapid cure systems is outlined. The experimental conditions where grafting may occur during radiation rapid cure processing are discussed. Possible future developments of the technique are outlined. 1 figure, 8 tables.

  1. Argon Plasma-Induced Graft Polymerization of PEGMA on Chitosan Membrane Surface for Cell Adhesion Improvement

    NASA Astrophysics Data System (ADS)

    Yin, Shiheng; Ren, Li; Wang, Yingjun

    2013-10-01

    For its biocompatibility and biodegradability, chitosan has had considerable attention for biomedical applications in recent years. In this paper, polymerization of poly (ethylene glycol) methyl ether methacrylate (PEGMA) was grafted onto chitosan membrane surface through argon plasma-induced graft polymerization. The surface properties after modification were characterized by contact angle measurement, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. The results indicated that PEGMA can be grafted successfully onto chitosan membrane surface. The surface hydrophilicity and free energy were improved and the surface roughness increased after modification. The adhesion of a human corneal epithelial cell (HCEC) on chitosan membrane surface was enhanced due to improvement of surface free energy and roughness.

  2. Immobilization of peroxidase on SPEU film via radiation grafting

    NASA Astrophysics Data System (ADS)

    Hongfei, Ha; Guanghui, Wang; Jilan, Wu

    The acrylic acid or acrylamide were grafted via radiation onto segmented polyetherurethane (SPEU) film which is a kind of biocompatible material. Then the Horse radish peroxidase was immobilized on the grafted SPEU film through chemical binding. Some quantitative relationships between the percent graft and the activity, amount of immobilized enzyme were given. The properties and application of obtained biomaterial was studied as well.

  3. R&D for graft adsorbents by radiation processing

    NASA Astrophysics Data System (ADS)

    Seko, Noriaki; Tamada, Masao

    Fibrous adsorbent for removal and recovery of metal ions have been synthesized by graft polymerization. In the grafting, the functional groups which have high selectivity against for target metal ions such as Fe, Sc, As, and U are introduced onto nonwoven fabric. When the monomer has a chelate group which makes selective coordination bond to specific these ions, it was directly grafted on the trunk polymer. In the case of precursor monomer having functional groups such as epoxy ring, the grafted trunk fabric is chemically modified. The resultant fibrous adsorbent leads the swift adsorption of metal ions. This property by using fibrous material can reduce the column size of adsorbent in the purification of waste water. The size of purification equipment becomes quite compact and that implies total volume of equipment can reduce. Instead of organic solvent, emulsion system which disperses monomer micelles in water with assistance of surfactant was found to accelerate the graft polymerization. This means the air pollution from organic solvent can be avoided by water system grafting. Furthermore, since the emulsion grafting was highly efficient, the required irradiation dose was considerably lower compared to general organic solvent system. As a result, the emulsion grafting has enormous potential for natural polymer to use as a trunk material for grafting. If a natural polymer such as cellulose can be used, the dependence on petroleum resources, the amount of industrial waste and the generation of carbon dioxide will be reduced to some extent.

  4. Membrane surface modification via polymer grafting and interfacial polymerization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Membrane separation is an important technology for separating food ingredients and fractionating high-value substances from food processing by-products. Long-term uses of polymeric membranes in food protein processing are impeded by formation of fouled layers on the membrane surface. Surface modif...

  5. The effects of early postoperative radiation on vascularized bone grafts

    SciTech Connect

    Evans, H.B.; Brown, S.; Hurst, L.N. )

    1991-06-01

    The effects of early postoperative radiation were assessed in free nonvascularized and free vascularized rib grafts in the canine model. The mandibles of one-half of the dogs were exposed to a cobalt 60 radiation dose of 4080 cGy over a 4-week period, starting 2 weeks postoperatively. The patency of vascularized grafts was confirmed with bone scintigraphy. Histological studies, including ultraviolet microscopy with trifluorochrome labeling, and histomorphometric analyses were performed. Osteocytes persist within the cortex of the vascularized nonradiated grafts to a much greater extent than in nonvascularized, nonradiated grafts. Cortical osteocytes do not persist in either vascularized or nonvascularized grafts subjected to radiation. New bone formation is significantly retarded in radiated grafts compared with nonradiated grafts. Periosteum and endosteum remained viable in the radiated vascularized grafts, producing both bone union and increased bone turnover, neither of which were evident to any significant extent in nonvascularized grafts. Bone union was achieved in vascularized and non-vascularized nonradiated bone. In the radiated group of dogs, union was only seen in the vascularized bone grafts.

  6. Radiation grafting of styrene on starch with high efficiency

    NASA Astrophysics Data System (ADS)

    Sheikh, N.; Akhavan, A.; Ataeivarjovi, E.

    2013-04-01

    Wheat starch grafted with polystyrene (PS-g-starch) was synthesized via polymerization grafting of styrene on starch by gamma-ray. The effects of starch/styrene weight ratio, and amount of applied doses (5-40 kGy) on the percentage of grafting, G (%), were investigated. The results showed that G (%) increased with increasing starch content. The optimum condition, starch/styrene weight ratio 1/3 and the applied dose 10 kGy, led to 252.9% of grafting. The obtained graft copolymer was characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, and scanning electron microscopy. FTIR spectroscopy as well as the XRD analysis exhibited the changes in chemical and crystalline structure of starch after grafting reaction. TGA demonstrated the changes in thermal stability of PS-g-starch copolymer. SEM micrographs indicated porous patches of PS adhering on the starch.

  7. Preparation and Characterization of Polymeric Surfactants Based on Epoxidized Soybean Oil Grafted Hydroxyethyl Cellulose.

    PubMed

    Huang, Xujuan; Liu, He; Shang, Shibin; Rao, Xiaoping; Song, Jie

    2015-10-21

    Epoxidized soybean oil (ESO) grafted hydroxyethyl cellulose (HEC) was prepared via ring-opening polymerization, in which the hydroxyl groups of HEC acted as initiators and the polymeric ESO were covalently bonded to the HEC. Hydrolysis of ESO-grafted HEC (ESO-HEC) was performed with sodium hydroxide, and the hydrolyzed ESO-HEC (H-ESO-HEC) products were characterized via Fourier transform infrared (FT-IR) and (1)H and (13)C nuclear magnetic resonance (NMR) spectroscopies, high-temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The results indicated that ring-opening polymerization of ESO occurred with the hydroxyl groups of HEC as initiators. The molecular weights of the H-ESO-HEC products were varied by adjusting the mass ratio of HEC and ESO. Through neutralizing the carboxylic acid of H-ESO-HEC with sodium hydroxide, novel polymeric surfactants (H-ESO-HEC-Na) were obtained, and the effects of polymeric surfactants on the surface tension of water were investigated as a function of concentration of H-ESO-HEC-Na. The H-ESO-HEC-Na was effective at lowering the surface tension of water to 26.33 mN/m, and the critical micelle concentration (CMC) value decreased from 1.053 to 0.157 g/L with increases in molecular weights of the polymeric surfactants. Rheological measurements indicated that the H-ESO-HEC-Na solutions changed from pseudoplastic property to Newtonian with increasing shear rate. PMID:26416659

  8. Antimicrobial hydantoin-grafted poly(ε-caprolactone) by ring-opening polymerization and click chemistry.

    PubMed

    Tan, Licheng; Maji, Samarendra; Mattheis, Claudia; Chen, Yiwang; Agarwal, Seema

    2012-12-01

    Novel degradable and antibacterial polycaprolactone-based polymers are reported in this work. The polyesters with pendent propargyl groups are successfully prepared by ring-opening polymerization and subsequently used to graft antibacterial hydantoin moieties via click chemistry by a copper(I)-catalyzed azide-alkyne cycloaddition reaction. The well-controlled chemical structures of the grafted copolymers and its precursors are verified by FT-IR spectroscopy, NMR spectroscopy, and GPC characterizations. According to the DSC and XRD results, the polymorphisms of these grafted copolymers are mostly changed from semicrystalline to amorphous depending on the amount of grafted hydantoin. Antibacterial assays are carried out with Bacillus subtilis and two strains of Escherichia coli and show fast antibacterial action. PMID:23008215

  9. A short review of radiation-induced raft-mediated graft copolymerization: A powerful combination for modifying the surface properties of polymers in a controlled manner

    NASA Astrophysics Data System (ADS)

    Barsbay, Murat; Güven, Olgun

    2009-12-01

    Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly γ radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of γ radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of γ radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.

  10. Pre-irradiation induced emulsion co-graft polymerization of acrylonitrile and acrylic acid onto a polyethylene nonwoven fabric

    NASA Astrophysics Data System (ADS)

    Liu, Hanzhou; Yu, Ming; Ma, Hongjuan; Wang, Ziqiang; Li, Linfan; Li, Jingye

    2014-01-01

    A pre-irradiation induced emulsion co-graft polymerization method was used to introduce acrylonitrile and acrylic acid onto a PE nonwoven fabric. The use of acrylic acid is meant to improve the hydrophilicity of the modified fabric. The kinetics of co-graft polymerization were studied. The existence of polyacrylonitrile (PAN) and poly(acrylic acid) (PAAc) graft chains was proven by Fourier transform infrared spectroscopy (FTIR) analysis. The existence of the nitrile groups in the graft chains indicates that they are ready for further amidoximation and adsorption of heavy metal ions.

  11. Polymerization Induced Self-Assembly of Alginate Based Amphiphilic Graft Copolymers Synthesized by Single Electron Transfer Living Radical Polymerization.

    PubMed

    Kapishon, Vitaliy; Whitney, Ralph A; Champagne, Pascale; Cunningham, Michael F; Neufeld, Ronald J

    2015-07-13

    Alginate-based amphiphilic graft copolymers were synthesized by single electron transfer living radical polymerization (SET-LRP), forming stable micelles during polymerization induced self-assembly (PISA). First, alginate macroinitiator was prepared by partial depolymerization of native alginate, solubility modification and attachment of initiator. Depolymerized low molecular weight alginate (∼12 000 g/mol) was modified with tetrabutylammonium, enabling miscibility in anhydrous organic solvents, followed by initiator attachment via esterification yielding a macroinitiator with a degree of substitution of 0.02, or 1-2 initiator groups per alginate chain. Then, methyl methacrylate was polymerized from the alginate macroinitiator in mixtures of water and methanol, forming poly(methyl methacrylate) grafts, prior to self-assembly, of ∼75 000 g/mol and polydispersity of 1.2. PISA of the amphiphilic graft-copolymer resulted in the formation of micelles with diameters of 50-300 nm characterized by light scattering and electron microscopy. As the first reported case of LRP from alginate, this work introduces a synthetic route to a preparation of alginate-based hybrid polymers with a precise macromolecular architecture and desired functionalities. The intended application is the preparation of micelles for drug delivery; however, LRP from alginate can also be applied in the field of biomaterials to the improvement of alginate-based hydrogel systems such as nano- and microhydrogel particles, islet encapsulation materials, hydrogel implants, and topical applications. Such modified alginates can also improve the function and application of native alginates in food and agricultural applications. PMID:26068280

  12. Enhanced microwave absorption performance of polyaniline-coated CNT hybrids by plasma-induced graft polymerization

    NASA Astrophysics Data System (ADS)

    Cheng, Junye; Zhao, Bin; Zheng, Shiyou; Yang, Junhe; Zhang, Deqing; Cao, Maosheng

    2015-04-01

    Highly conducting CNT/polyaniline hybrids were prepared by plasma-induced graft polymerization, i.e., plasma pretreatment of CNTs and further in situ polymerization of aniline. Plasma pretreatment made more aniline grafted on the CNTs' surface by the role of oxygen radicals. SEM images showed that the surfaces of CNTs were uniformly coated by PANI. FTIR showed that there was presence of strong interaction between CNTs and PANI molecular chains. The conductivity of CNT/PANI hybrids with plasma treatment is higher than that of CNT/PANI hybrids without plasma pretreatment (0.443 S/cm at 0 W) or pretreated by acid oxidation method. Importantly, the microwave absorption properties were investigated by measuring complex permeability, complex permittivity and reflection loss in a frequency of 2-18 GHz. The microwave absorption enhancement of CNT/PANI hybrids results mainly from dielectric loss rather than magnetic loss due to higher value of dielectric loss.

  13. Plasma polymerized thin coating as a protective layer of carbon nanotubes grafted on carbon fibers

    NASA Astrophysics Data System (ADS)

    Einig, A.; Rumeau, P.; Desrousseaux, S.; Magga, Y.; Bai, J. B.

    2013-04-01

    Nanoparticles addition is widely studied to improve properties of carbon fiber reinforced composites. Here, hybrid carbon fiber results from grafting of carbon nanotubes (CNT) by Chemical Vapor Deposition (CVD) on the carbon fiber for mechanical reinforcement and conductive properties. Both tows and woven fabrics made of the hybrid fibers are added to the matrix for composite processing. However handling hybrid fibers may induce unwilling health risk due to eventual CNT release and a protective layer is required. A thin coating layer is deposited homogeneously by low pressure plasma polymerization of an organic monomer without modifying the morphology and the organization of grafted CNTs. The polymeric layer effect on the electrical behavior of hybrid fiber is assessed by conductivity measurements. Its influence on the mechanical properties is also studied regarding the interface adhesion between fiber and matrix. The protective role of layer is demonstrated by means of friction constraints applied to the hybrid fiber.

  14. Insolubilisation of biologically active materials with novel radiation graft copolymers

    NASA Astrophysics Data System (ADS)

    Garnett, J. L.; Jankiewicz, S. V.; Levot, R.; Sangster, D. F.

    The use of radiation grafting to immobilise a typical enzyme, trypsin, is reported. The technique involves radiation grafting to a backbone polymer a monomer containing an appropriate functional group to which the enzyme is bonded. In the present work, p-nitrostyrene has been grafted to representative trunk polymers, polypropylene and PVC, the nitro group in the resulting copolymer converted to the isothiocyanato derivative to which trypsin is attached. Of importance to this insolubilisation process, especially for radiation sensitive backbone polymers, is the inclusion of additives which enhance grafting. A new class of additives which increase the grafting yields is reported using as representative backbone polymers, naturally occurring cellulose and synthetic low density polyethylene. The new additives are specific metal salts such as LiClO 4. The reactivity of these salts in grafting enhancement has been compared with that of mineral acid which has previously been used as an additive to increase grafting yields in both preirradiation and simultaneous techniques. A new model for grafting enhancement in the presence of the metal salts as well as acids is proposed whereby increased grafting yields are attributed to increased partitioning of monomer into the graft region in the presence of ionic solutes. The value of these additives in preparing copolymers suitable for general reagent insolubilisation reactions is discussed.

  15. Gamma radiation-induced grafting of glycidyl methacrylate (GMA) onto water hyacinth fibers

    NASA Astrophysics Data System (ADS)

    Madrid, Jordan F.; Nuesca, Guillermo M.; Abad, Lucille V.

    2013-04-01

    Water hyacinth fibers (Eichhornia crassipes) were functionalized using radiation-induced graft polymerization of glycidyl methacrylate by γ-rays from 60Co source. The simultaneous grafting technique was employed wherein the water hyacinth fibers were irradiated in nitrogen atmosphere in the presence of glycidyl methacrylate dissolved in water/methanol solvent. The effects of different grafting parameters to the grafting yield were evaluated. The optimal values of solvent, absorbed dose, dose rate, and concentration of monomer were found to be 1:3 (volume/volume) water-methanol solvent, 10 kGy, 8 kGy h-1 dose rate and 5% volume/volume glycidyl methacrylate, respectively. Using the optimum conditions, degree of grafting of approximately 58% was achieved. The grafted water hyacinth fibers were characterized using Attenuated Total Reflectance-Fourier Transformed Infrared Spectroscopy (ATR-FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX). The results of these tests confirmed the successful grafting of glycidyl methacrylate onto water hyacinth fibers.

  16. Graft Polymerization of Acrylic Acid on a Polytetrafluoroethylene Panel by an Inductively Coupled Plasma

    NASA Astrophysics Data System (ADS)

    Lan, Yan; You, Qingliang; Cheng, Cheng; Zhang, Suzhen; Ni, Guohua; Nagatsu, M.; Meng, Yuedong

    2011-02-01

    Surface modification on a polytetrafluoroethylene (PTFE) panel was performed with sequential nitrogen plasma treatments and surface-initiated polymerization. By introducing COO- groups to the surface of the PTFE panel through grafting polymerization of acrylic acid (AA), a transparent poly (acrylic acid) (PAA) membrane was achieved from acrylic acid solution. Grafting polymerization initiating from the active groups was achieved on the PTFE panel surface after the nitrogen plasma treatment. Utilizing the acrylic acid as monomers, with COO- groups as cross link sites to form reticulation structure, a transparent poly (acrylic acid) membrane with arborescent macromolecular structure was formed on the PTFE panel surface. Analysis methods, such as fourier transform infrared spectroscopy (FTIR), microscopy and X-ray photoelectron spectroscopy (XPS), were utilized to characterize the structures of the macromolecule membrane on the PTFE panel surface. A contact angle measurement was performed to characterize the modified PTFE panels. The surface hydrophilicities of modified PTFE panels were significantly enhanced after the plasma treatment. It was shown that the grafting rate is related to the treating time and the power of plasma.

  17. Enhanced biocompatibility of polyphosphazenes achieved by radiation grafting

    NASA Astrophysics Data System (ADS)

    Carenza, M.; Lora, S.; Palma, G.; Pezzin, G.; Caliceti, P.

    1996-08-01

    This paper reviews the work recently carried out in the authors' laboratory on the radiation graft copolymerization of hydrophilic monomers onto polyphosphazenes. Kinetics of grafting by the mutual irradiation method at room temperature of monomer-solvent mixtures were followed. Hydrophilicity, structure, mechanical properties, biocompatibility and anticoagulating properties of the modified samples were reported. Some experiments on the grafted polymer, to which heparin was ionically bonded with a high yield, were also carried out.

  18. "Grafting-from" polymerization of PMMA from stainless steel surfaces by a RAFT-mediated polymerization process.

    PubMed

    Zammarelli, Nico; Luksin, Michael; Raschke, Hannes; Hergenröder, Roland; Weberskirch, Ralf

    2013-10-15

    The synthesis of grafted PMMA homopolymer films is reported using a surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization from a RAFT-agent immobilized on a silanized stainless steel surface. Therefore, stainless steel surfaces were hydroxylated with piranha solution followed by silanization with 3-aminopropylsilane (APS). The pendant primary amino groups of the cross-linked polysiloxane layer were reacted with 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid N-hydroxysuccinimide ester to produce a surface with covalently immobilized RAFT agents. PMMA homopolymers of different molecular weights between 13 060 and 45 000 g/mol were then prepared by a surface-initiated RAFT polymerization. Molecular weight (MW) and polydispersity index (PDI) were determined from sacrificial polymerization in solution. The different steps of stainless steel surface modification and the ultrathin films were investigated using atomic force microscopy (AFM), static, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance infrared spectroscopy (ATR-IR), and ellipsometry. PMID:24053195

  19. Utilizing advanced polymerization techniques for simplifying polymer grafting from silica colloidal crystal substrates

    NASA Astrophysics Data System (ADS)

    Yerneni, Charu K.

    Polyacrylamide has been well established as a biocompatible material when Polyacrylamide gel electrophoresis (PAGE) came into existence in the 1960s. Under aqueous buffer conditions it becomes non-adsorptive to proteins and due to its molecular level pore forming nature could be used in size based biomolecule separations. Since then considerable research has been done to explore the non-adsorptive nature of polyacrylamide on a platform or substrate. Attempts were made to grow polyacrylamide chains from silica as a substrate which can then be used in various protein separation techniques. Based on an ionic polymerization method which was used for gel casting in PAGE, polymers were grown on silica gel. Though considerable thickness could be achieved, polymerization was not just confined to the surface. Therefore a rigid polymer brush layer could not be achieved. Atom transfer radical polymerization (ATRP) method showed the solution to this problem. Polymer brush layers with acceptable thickness could now be achieved for growing polyacrylamide from silica gel. Yet it still suffered from several disadvantages such as the need of an inert atmosphere for polymerization and limited thickness. Many developments have taken place in the past decade which led to improvements in substrate and polymerization methods. This research used non porous sub-micron silica as the substrate and AGET ATRP (Activator generated electron transfer atom transfer radical polymerization) for surface grafting polyacrylamide. Non porous submicron silica has been shown to be a better stationary phase substrate for protein separations than conventional substrates. AGET ATRP enables polymerization to be performed under ambient conditions and in water based solutions which gives thicknesses much higher than conventional ATRP. Data from various analytical techniques showed that within the experimental range the polymerization is linear and has decent control. This means silica nanoparticles coated with polyacrylamide of varying thickness can be produced by varying the reaction time. Linear polymerization kinetics was studied using IR spectroscopy, elemental analysis, ellipsometry, GPC etc. All of them closely agree with each other. Attempts were made to expand the applicability of this novel way of material synthesis. HILIC is known as a premium separation mode for polar analytes. Glycoproteins form an important class of analytes which need better separation columns. Polyacrylamide coated nonporous colloidal silica is shown here to be a better column packing material. Combined results show that AGET ATRP can be a better and simpler alternative to ATRP for grafting polyacrylamide onto silica based substrates. Future efforts can possibly lead to the expansion of the applicability of this method for making materials for many other separation methods.

  20. Radiation polymerization in the emulsion systems

    NASA Astrophysics Data System (ADS)

    Sundardi, F.; Zubir, A.; Marliyanti, I.

    Kinetics aspects of radiation polymerization of methyl-methacrylate, styrene and vinyl acetate monomers in the emulsion systems have been studied. A panoramic gamma source with an activity of about 70,000 Ci was employed as a variable dose rate irradiator. Influence of the emulsifier content and irradiation dose rate on the rate of polymerization and the molecular weight of the products have been studied. In this study, Smith-Ewart rate theory was used to explain the experimental results. Tween 20 was used as the emulsifier. In the case of vinyl acetate monomer, it was found that the irradiation dose needed for obtaining a certain degree of conversion increased with the increase of the emulsifier content. However, in the case of styrene and methylmethacrylate monomers it was found that the irradiation dose needed for obtaining a certain degree of conversion decreased with the increase of the emulsifier content. The molecular weight of polymers, were found to be much influenced by the irradiation dose rate, emulsifier content and the degree of conversion. It was found that the three monomers showed different characteristics. Several deviation from Smith-Ewart rate theory have been detected.

  1. Radiation polymerization of thermo-sensitive poly ( N-vinylcaprolactam)

    NASA Astrophysics Data System (ADS)

    Cheng, S. C.; Feng, W.; Pashikin, I. I.; Yuan, L. H.; Deng, H. C.; Zhou, Y.

    2002-03-01

    Temperature-sensitive poly ( N-vinylcaprolactam) both in water-soluble state and in gel was prepared by γ-radiation polymerization. The effects of radiation dose, radiation dose rate and monomer concentration on polymerization and the low critical solution temperature characteristics of the polymer were studied. The results show that the polymer prepared within certain radiation dose (beyond 2 kGy) and dose rate range (2-14 Gy/min) has good temperature sensitivity and uniformity.

  2. Study of plasma-induced graft polymerization of stearyl methacrylate on cotton fabric substrates

    NASA Astrophysics Data System (ADS)

    Li, Yongqiang; Zhang, Yan; Zou, Chao; Shao, Jianzhong

    2015-12-01

    A simple and facile method to prepare the cotton fabric with hydrophobicity was described in the present work. In the one-step process, the cotton fabric pre-impregnated with the monomer solution of stearyl methacrylate (SMA) was placed in the plasma chamber and followed by glow discharge of the Helium low temperature plasma. The cotton fabrics before and after the plasma treatment were characterized by field emission scanning electron microscopy (FESEM), infrared spectroscopic analysis (FTIR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA), respectively. The wettability of the cotton fabrics was evaluated by contact angle measurement. Fabric Hand Values and mechanical properties were also measured in the experiment. The results showed that polymer films could be coated on the cotton fibers through the plasma induced grafting polymerization of SMA. The modified cotton fabrics exhibited an extraordinary hydrophobicity with a contact angle of 149° for a 5 μL water droplet and excellent thermal stability. The relative hand value and mechanical breaking strength of the cotton fabrics declined slightly after graft polymerization of SMA by the plasma.

  3. PEG Molecular Net-Cloth Grafted on Polymeric Substrates and Its Bio-Merits

    NASA Astrophysics Data System (ADS)

    Zhao, Changwen; Lin, Zhifeng; Yin, Huabing; Ma, Yuhong; Xu, Fujian; Yang, Wantai

    2014-05-01

    Polymer brushes and hydrogels are sensitive to the environment, which can cause uncontrolled variations on their performance. Herein, for the first time, we report a non-swelling ``PEG molecular net-cloth'' on a solid surface, fabricated using a novel ``visible light induced surface controlled graft cross-linking polymerization'' (VSCGCP) technique. Via this method, we show that 1) the 3D-network structure of the net-cloth can be precisely modulated and its thickness controlled; 2) the PEG net-cloth has excellent resistance to non-specific protein adsorption and cell adhesion; 3) the mild polymerization conditions (i.e. visible light and room temperature) provided an ideal tool for in situ encapsulation of delicate biomolecules such as enzymes; 4) the successive grafting of reactive three-dimensional patterns on the PEG net-cloth enables the creation of protein microarrays with high signal to noise ratio. Importantly, this strategy is applicable to any C-H containing surface, and can be easily tailored for a broad range of applications.

  4. Homogeneous ring opening graft polymerization of ɛ-caprolactone onto xylan in dual polar aprotic solvents.

    PubMed

    Zhang, Xueqin; Chen, Mingjie; Liu, Chuanfu; Zhang, Aiping; Sun, Runcang

    2015-03-01

    Homogeneous ring-opening graft polymerization (ROGP) of ɛ-caprolactone (ɛ-CL) onto xylan was investigated in dual polar aprotic solvents, N,N-dimethylformamide/lithium chloride (DMF/LiCl), N,N-dimethylacetamide/LiCl (DMAc/LiCl), and 1-methyl-2-pyrrolidinone/LiCl (NMP/LiCl). The effects of reaction solvents, temperature, and the molar ratio of ɛ-CL to anhydroxylose units (AXU) on the degree of substitution (DS) of xylan-graft-poly(ɛ-caprolactone) (xylan-g-PCL) copolymers and the degree of polymerization (DP) of the attached PCL side chains were investigated. FT-IR and NMR analyses provided the evidence of the occurrence of ROGP reaction. The thermal stability of xylan increased upon ROGP reaction due to the increased length of PCL side chains. With the increased attachment of PCL side chains, the tensile strength and Young's modulus of the films decreased, whereas the elongation at break increased. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations provided the evidences of the increased film properties due to the attachment of PCL side chains. PMID:25498691

  5. Radiation polymerization of diethyl fumarate [rapid communication

    NASA Astrophysics Data System (ADS)

    Alkassiri, Haroun

    2005-05-01

    Diethyl fumarate (DEF) has been polymerized by gamma irradiation using doses in the range 50-300 kGy, and in this dose range the polymerization yield increased almost linearly. The polymer has a glass transition temperature of about -20 °C, softening point about 15 °C, and decomposition temperature 300 °C.

  6. Surface graft polymerization of SU-8 for bio-MEMS applications

    NASA Astrophysics Data System (ADS)

    Wang, Yuli; Pai, Jeng-Hao; Lai, Hsuan-Hong; Sims, Christopher E.; Bachman, Mark; Li, G. P.; Allbritton, Nancy L.

    2007-07-01

    There is currently increasing interest in using SU-8 photoresist to build microstructures for micro-electro-mechanical systems (MEMS). This report describes an effective bench-top method to modify the surface properties of SU-8 photoresist. This strategy relies on the residual epoxide groups present on the surface of SU-8 following fabrication. These epoxide groups are converted into hydroxyl groups by oxidation with a high concentration of cerium(IV) ammonium nitrate (CAN) and nitric acid. Subsequently the surface hydroxyl groups are used as initiation sites for graft polymerization catalyzed by CAN in the presence of acid. A number of water-soluble polymers including poly(acrylic acid), poly(acrylamide), poly(ethylene glycol) were successfully grafted onto SU-8. The presence of surface-linked polymers was confirmed by contact angle measurements, attenuated total reflection-Fourier transform infrared spectroscopy and toluidine blue adsorption. This method was particularly useful for tailoring the surface properties of complex or enclosed microstructures, for example, microfluidic channels. In addition the grafted polymers could serve as sites for high density protein immobilization or cell attachment on Bio-MEMS.

  7. A mild strategy to encapsulate enzyme into hydrogel layer grafted on polymeric substrate.

    PubMed

    Zhu, Xing; Ma, Yuhong; Zhao, Changwen; Lin, Zhifeng; Zhang, Lihua; Chen, Ruichao; Yang, Wantai

    2014-12-23

    Although the hydrogel network has been widely investigated as a carrier for enzyme immobilization, to in situ encapsulate enzymes into a hydrogel network in an efficient, practical, and active way is still one of the great challenges in the field of biochemical engineering. Here, we report a new protocol to address this issue by encapsulating enzyme into poly(ethylene glycol) (PEG) hydrogel network grafted on polymeric substrates. In our strategy, isopropyl thioxanthone semipinacol (ITXSP) dormant groups were first planted onto the surface of a plastic matrix with low density polyethylene (LDPE) film as a model by a UV-induced abstracting hydrogen-coupling reaction. As a proof of concept, lipase, which could catalyze esterification of glucose with palmitic acid, then was in situ net-immobilized into a PEG-based hydrogel network layer through a visible light-induced surface controlled/living graft cross-linking polymerization. This strategy demonstrates the following novel significant merits: (1) in comparison with the UV irradiation or high temperature, the visible light and room temperature used provide a friendly condition to maintain activity of enzyme during immobilization; (2) the uniqueness of controlled/living cross-linking polymerization not only makes it easy to form a uniform PEG hydrogel network, which is a benefit to avoid the leakage of net-immobilizing enzyme, but also to tune the net-thickness or capacity to accommodate enzyme; and (3) as compared to systems of nanoparticles and porous matrixes, the flexible/robust end-products of the surface net-immobilizing enzyme with polymer film are more suitable to be applied in a bioreactor due to their features of easier separation and reuse. We confirmed that this catalytic film could retain almost all of its initial activity after seven batches of 24 h esterifications. The proposed strategy provides an extremely simple, effective, and flexible method for enzyme immobilization. PMID:25489918

  8. Strategies and Techniques to Enhance the In Situ Endothelialization of Small-Diameter Biodegradable Polymeric Vascular Grafts

    PubMed Central

    Hibino, Narutoshi; Fisher, John P.

    2013-01-01

    Due to the lack of success in small-diameter (<6 mm) prosthetic vascular grafts, a variety of strategies have evolved utilizing a tissue-engineering approach. Much of this work has focused on enhancing the endothelialization of these grafts. A healthy, confluent endothelial layer provides dynamic control over homeo-stasis, influencing and preventing thrombosis and smooth muscle cell proliferation that can lead to intimal hyperplasia. Strategies to improve endothelialization of biodegradable polymeric grafts have encompassed both chemical and physical modifications to graft surfaces, many focusing on the recruitment of endothelial and endothelial progenitor cells. This review aims to provide a compilation of current and developing strategies that utilize in situ endothelialization to improve vascular graft outcomes, providing a context for the future directions of vascular tissue-engineering strategies that do not require preprocedural cell seeding. PMID:23252992

  9. Invertase immobilization onto radiation-induced graft copolymerized polyethylene pellets

    NASA Astrophysics Data System (ADS)

    de Queiroz, Alvaro Antonio Alencar; Vitolo, Michele; de Oliveira, Rômulo Cesar; Higa, Olga Zazuco

    1996-06-01

    The graft copolymer poly(ethylene-g-acrylic acid) (LDPE-g-AA) was prepared by radiation-induced graft copolymerization of acrylic acid onto low density polyethylene (LDPE) pellets, and characterized by infrared photoacoustic spectroscopy and scanning electron microscopy (SEM). The presence of the grafted poly(acrylic acid) (PAA) was established. Invertase was immobilized onto the graft polymer and the thermodynamic parameters of the soluble and immobilized enzyme were determined. The Michaelis constant, Km, and the maximum reaction velocity, Vmax, were determined for the free and the immobilized invertase. The Michaelis constant, Km was larger for the immobilized invertase than for the free enzyme, whereas Vmax was smaller for the immobilized invertase. The thermal stability of the immobilized invertase was higher than that of the free enzyme.

  10. Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy.

    PubMed

    Radzinski, Scott C; Foster, Jeffrey C; Matson, John B

    2016-04-01

    Bottlebrush polymers are synthesized using a tandem ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well-defined bottlebrush polymers with molecular weights in excess of 10(6) Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d,l-lactide initiated by an alcohol-functionalized norbornene. ROMP grafting-through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size-exclusion chromatographic and (1) H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain-free transmission electron microscopy on graphene oxide. PMID:26847467

  11. Design of pervaporation membrane for organic-liquid separation based on solubility control by plasma-graft filling polymerization technique

    SciTech Connect

    Yamaguchi, Takeo; Nakao, Shinichi; Kimura, Shoji )

    1993-05-01

    Pervaporation performance through the membranes showed the same tendency as solubility results. The authors have prepared the filling-polymerized membrane for pervaporation of organic-liquid mixtures by the plasma-graft polymerization technique. The membrane is composed of two different polymers: a porous substrate which can suppress membrane swelling and a grafted polymer which forms in the pores of the substrate and exhibits selectivity due to its solubility. The objectives of the present study are to design a suitable membrane for an organic-mixture system by the control of the filling-polymer solubility. Specifically, a porous high-density polyethylene membrane and poly(methylacrylate/acrylamide) copolymer were employed as the porous substrate and grafted polymer, respectively, and grafted copolymer solubility was predicted by Hansen solubility parameters (HSP). The grafted polymer composition and its solubility behavior could be controlled by varying the monomer composition, and the solubility change was in accordance with the prediction by HSP. Pervaporation performance through the membranes showed the same tendency as solubility results. The authors concluded that an optimum pervaporation membrane can be designed on the basis of solubility control through use of these techniques for polymerization and prediction.

  12. Anti-Biofouling Effect of PEG-Grafted Block Copolymer Synthesized by RAFT Polymerization.

    PubMed

    Kim, Seon-Mi; Han, Sang Suk; Kim, A Young; Choi, Beom-Jin; Paik, Hyun-Jong; Lee, Inwon; Park, Hyun; Chun, Ho Hwan; Cho, Youngjin; Hwang, Do-Hoon

    2015-10-01

    Poly(glycidyl methadrylate-block-styrene) (PGMA-b-PS), a block copolymer consisting of glycidyl methacrylate and styrene, was synthesized via reversible addition-fragmentation chain transfer living polymerization. The synthesized PGMA-b-PS was then grafted with low-molecular-weight polyethylene glycol (PEG) via epoxy ring opening to give PGMA-g-PEG-b-PS, which was evaluated as an anti-biofouling coating material. As a preliminary test for the anti-biofouling effect, a protein adsorption experiment was performed on the synthesized block copolymer surface. The block copolymers were spin-coated onto silicon wafers, and protein adsorption experiments were carried out using fluorescein isothiocyanate conjugate-labeled bovine serum albumin. The fluorescence intensity of the protein adsorbed on the block copolymer surface was compared with that of a polystyrene film as a reference. The synthesized PGMA-g-PEG-b-PS film showed much lower fluorescence intensity than that of the PS film. PMID:26726430

  13. Ring-opening graft polymerization of propylene carbonate onto xylan in an ionic liquid.

    PubMed

    Zhang, Xueqin; Chen, Mingjie; Liu, Chuanfu; Zhang, Aiping; Sun, Runcang

    2015-01-01

    The amidine organocatalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst. Biocomposites with tuneable properties were successfully synthesized by ring-opening graft polymerization (ROGP) of propylene carbonate (PC) onto xylan using DBU as a catalyst in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time and the molar ratio of PC to anhydroxylose units (AXU) in xylan were investigated. The physico-chemical properties of xylan-graft-poly(propylene carbonate) (xylan-g-PPC) copolymers were characterised by FT-IR, NMR, TGA/DTG, AFM and tensile analysis. The FT-IR and NMR results indicated the successful attachment of PPC onto xylan. TGA/DTG suggested the increased thermal stability of xylan after the attachment of PPC side chains. AFM analysis revealed details about the molecular aggregation of xylan-g-PPC films. The results also showed that with the increased DS of xylan-g-PPC copolymers, the tensile strength and Young's modulus of the films decreased, while the elongation at break increased. PMID:25853319

  14. PEG Molecular Net-Cloth Grafted on Polymeric Substrates and Its Bio-Merits

    PubMed Central

    Zhao, Changwen; Lin, Zhifeng; Yin, Huabing; Ma, Yuhong; Xu, Fujian; Yang, Wantai

    2014-01-01

    Polymer brushes and hydrogels are sensitive to the environment, which can cause uncontrolled variations on their performance. Herein, for the first time, we report a non-swelling “PEG molecular net-cloth” on a solid surface, fabricated using a novel “visible light induced surface controlled graft cross-linking polymerization” (VSCGCP) technique. Via this method, we show that 1) the 3D-network structure of the net-cloth can be precisely modulated and its thickness controlled; 2) the PEG net-cloth has excellent resistance to non-specific protein adsorption and cell adhesion; 3) the mild polymerization conditions (i.e. visible light and room temperature) provided an ideal tool for in situ encapsulation of delicate biomolecules such as enzymes; 4) the successive grafting of reactive three-dimensional patterns on the PEG net-cloth enables the creation of protein microarrays with high signal to noise ratio. Importantly, this strategy is applicable to any C-H containing surface, and can be easily tailored for a broad range of applications. PMID:24845078

  15. Charge tunable zwitterionic polyampholyte layers formed in cyclic olefin copolymer microchannels through photochemical graft polymerization.

    PubMed

    Peng, Xianglu; Zhao, Lei; Du, Gangfeng; Wei, Xuan; Guo, Jinxiu; Wang, Xiayan; Guo, Guangsheng; Pu, Qiaosheng

    2013-02-01

    Zwitterionic layers immobilized on various surfaces exhibit ideal biocompatibility and antifouling capability, but direct immobilization of zwitterionic molecules provides limited choice of surface charges. In this paper, the formation of charge tunable zwitterionic polyampholyte layers onto the surface of microfluidic channels of cyclic olefin copolymer by photochemical graft polymerization of mixed acrylic monomers, [2-(acryloyloxy) ethyl] trimethyl ammonium chloride and 2-acrylamido-2-methyl-1-propanesulfonic, under UV illumination was reported. With this method, surface charge of the resulting modification layers could be tailored through the initial monomer ratio and reaction conditions. The incorporation of both monomers into the grafted layers was confirmed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection Fourier transform infrared (ATR-FTIR). The results indicate that the modified layers are hydrophilic with contact angles of 33.0-44.3°, and the isoelectric points of the modified layers can be tuned from <3 to >9 simply by adjusting the monomer ratios. Elimination of the nonspecific adsorption of proteins on the zwitterionic layers thus formed was proved by fluorescent microscopy and streaming potential measurement. The uniformity of the modified layers was verified through a comparison of electrophoresis inside the modified and native microchannels. A whole blood coagulation time measurement was performed to show its applicability. PMID:23331535

  16. Dual responsive polymeric nanoparticles prepared by direct functionalization of polylactic acid-based polymers via graft-from ring opening metathesis polymerization.

    PubMed

    Veccharelli, Kate M; Tong, Venus K; Young, Jennifer L; Yang, Jerry; Gianneschi, Nathan C

    2016-01-11

    Polylactic acid (PLA) has found widespread use in plastics and in biomedical applications due to its biodegradability into natural benign products. However, PLA-based materials remain limited in usefulness due to difficulty of incorporating functional groups into the polymer backbone. In this paper, we report a strategy for PLA functionalization that establishes the preparation of highly derivatized materials in which ring opening metathesis polymerization (ROMP) is employed as a graft-from polymerization technique utilizing a norbornene-modified handle incorporated into the PLA backbone. As a demonstration of this new synthetic methodology, a PLA-derived nanoparticle bearing imidazole units protected with a photolabile group was prepared. The morphology of this material could be controllably altered in response to exposure of UV light or acidic pH as a stimulus. We anticipate that this graft-from approach to derivatization of PLA could find broad use in the development of modified, biodegradable PLA-based materials. PMID:26541981

  17. Constructing doxorubicin-loaded polymeric micelles through amphiphilic graft polyphosphazenes containing ethyl tryptophan and PEG segments.

    PubMed

    Qiu, Li Yan; Yan, Mei Qiu

    2009-07-01

    By changing the molar ratio of hydrophilic and hydrophobic segments, a series of novel amphiphilic graft polyphosphazenes (PEG/EtTrp-PPPs) was synthesized via thermal ring-opening polymerization and a subsequent two-step substitution reaction of hydrophilic methoxyl polyethylene glycol (MPEG) and hydrophobic ethyl tryptophan (EtTrp). (1)H-Nuclear magnetic resonance and Fourier transform infrared studies validated the expected synthesis of copolymers. The copolymer composition was also confirmed by UV-visible spectrophotometry. The molar ratio of the segment PEG to group EtTrp was 1.33:0.67, 1.01:0.99 and 0.78:1.22, respectively. Micellization behavior of PEG/EtTrp-PPPs in an aqueous phase was characterized by fluorescence technique, dynamic light scattering and transmission electron microscopy. The critical micelle concentration (CMC) of the graft copolymer in aqueous solution was 0.158, 0.033 and 0.020gl(-1), which decreased as the hydrophobic content in amphiphilic copolymers increased. Doxorubicin (DOX) was physically loaded into micelles prepared by an O/W emulsion method with a drug loading content increasing with DOX feeding. In vitro release of DOX from micelles can be accelerated in weak acidic solution. The results of cytotoxicity study using an MTT assay method with HeLa cell showed that amphiphilic graft polyphosphazenes were biocompatible while DOX-loaded micelles achieved comparable cytotoxicity with that of free DOX. In summary, these novel amphiphilic copolymers exhibited potential to be used as injectable drug carriers for tumor treatment. PMID:19282261

  18. Radiation-induced grafting of acrylamide onto guar gum in aqueous medium: Synthesis and characterization of grafted polymer guar-g-acrylamide

    NASA Astrophysics Data System (ADS)

    Biswal, Jayashree; Kumar, Virendra; Bhardwaj, Y. K.; Goel, N. K.; Dubey, K. A.; Chaudhari, C. V.; Sabharwal, S.

    2007-10-01

    Mutual radiation grafting technique has been applied to carry out grafting of acrylamide (AAm) onto guar gum (GG) using high-energy Co 60γ radiation to enhance its flocculating properties for industrial effluents. The grafted product was characterized using analytical probes like elemental analysis, thermal analysis, Fourier transformed infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The grafting extent was observed to decrease with the dose rate and increase with the concentration of AAm. Thermo gravimetric analysis (TGA) of grafted and ungrafted samples indicated better stability of grafted product. γ and microwave radiation effect on grafted and virgin GG has also been reported.

  19. Polymeric nanocomposite proton exchange membranes prepared by radiation-induced polymerization for direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Kim, Young-Seok; Seo, Kwang-Seok; Choi, Seong-Ho

    2016-01-01

    The vinyl group-modified montmorillonite clay (F-MMT), vinyl group-modified graphene oxide (F-GO), and vinyl group-modified multi-walled carbon nanotube (F-MWNT) were first prepared by ion exchange reaction of 1-[(4-ethylphenyl)methyl]-3-butyl-imidazolium chloride in order to use the materials for protection against methanol cross-over in direct methanol fuel cell (DMFC) membrane. Then polymeric nanocomposite membranes with F-MMT, F-GO, and F-MWNT were prepared by the solvent casting method after radiation-induced polymerization of vinyl monomers in water-methanol mixture solvents. The proton conductivity, water uptake, ion-exchange capacity, methanol permeability, and DMFC performance of the polymeric nanocomposite membranes with F-MMT, F-GO, and F-MWNT were evaluated.

  20. Amine functionalized radiation-induced grafted water hyacinth fibers for Pb2+, Cu2+ and Cr3+ uptake

    NASA Astrophysics Data System (ADS)

    Madrid, Jordan F.; Nuesca, Guillermo M.; Abad, Lucille V.

    2014-04-01

    An amine group containing fibrous adsorbent was prepared by reaction of grafted water hyacinth fibers with ethylenediamine. Glycidyl methacrylate (GMA) was grafted onto water hyacinth fibers using gamma radiation induced graft polymerization through simultaneous grafting technique and this was used as base material for producing the amine type adsorbents. The conversion of the epoxy group from GMA into amine group was investigated. The concentration of ethylenediamine solution that gave the highest amine functional group density was 50% by volume in 2-propanol. The amine functionalized water hyacinth fibers were characterized using Attenuated Total Reflectance-Fourier Transformed Infrared Spectroscopy (ATR-FTIR), Thermogravimetric Analysis (TGA), and Energy Dispersive X-ray Spectroscopy (EDX). Information derived from these analyses confirms the successful conversion of the epoxy group. The amine-type adsorbent was evaluated for its uptake of Pb2+, Cu2+ and Cr3+ from aqueous solutions. The initial concentration of the metal ions and pH of the solutions were found to influence the amount of metal ions adsorbed by the amine-type adsorbent. The kinetics of adsorption was observed to follow Lagergren's first order equation. Results of ion sorption studies indicate that gamma radiation-induced grafting and subsequent chemical modification improved the ion sorption behaviour of water hyacinth fibers.

  1. Space radiation resistant transparent polymeric materials

    NASA Technical Reports Server (NTRS)

    Giori, C.; Yamauchi, T.

    1977-01-01

    A literature search in the field of ultraviolet and charged particle irradiation of polymers was utilized in an experimental program aimed at the development of radiation stable materials for space applications. The rationale utilized for material selection and the synthesis, characterization and testing performed on several selected materials is described. Among the materials tested for ultraviolet stability in vacuum were: polyethyleneoxide, polyvinylnaphthalene, and the amino resin synthesized by the condensation of o-hydroxybenzoguanamine with formaldehyde. Particularly interesting was the radiation behavior of poly(ethyleneoxide), irradiation did not cause degradation of optical properties but rather an improvement in transparency as indicated by a decrease in solar absorptance with increasing exposure time.

  2. Radiation grafted adsorbents for newly emerging environmental applications

    NASA Astrophysics Data System (ADS)

    Mahmoud Nasef, Mohamed; Ting, T. M.; Abbasi, Ali; Layeghi-moghaddam, Alireza; Sara Alinezhad, S.; Hashim, Kamaruddin

    2016-01-01

    Radiation induced grafting (RIG) is acquired to prepare a number of adsorbents for newly emerging environmental applications using a single route involving RIG of glycidymethacrylate (GMA) onto polyethylene-polypropylene (PE-PP) non-woven fabric. The grafted fabric was subjected to one of three functionalization reactions to impart desired ionic characters. This included treatment with (1) N-dimethyl-D-glucamine, (2) triethylamine and (3) triethylamine and alkalisation with KOH. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) were used to study the changes in chemical and physical structures of the obtained fibrous adsorbents. The potential applications of the three adsorbents for removal of boron from solutions, capturing CO2 from CO2/N2 mixtures and catalysing transesterification of triacetin/methanol to methyl acetate (biodiesel) were explored. The obtained fibrous adsorbents provide potential alternatives to granular resins for the investigated applications and require further development.

  3. Towards application of one- and two-dimensional nanomaterials for reinforcement of polymeric nanocomposite bone grafts

    NASA Astrophysics Data System (ADS)

    Farrshid, Behzad

    One- and two-dimensional (1-D and 2-D) nanomaterials possess extraordinary physiochemical properties such as large surface area, excellent mechanical properties, high surface energy and good dispersivity in organic and biological solvents, therefore, they have been extensively used as reinforcing agents to improve the mechanical properties of polymeric scaffolds for bone tissue engineering applications. Carbon nanomaterials such as carbon nanotubes and graphene have been used as reinforcing agents for biodegradable polymeric scaffolds and composites, however, their short- and long-term in vitro cytotoxicity and in vivo biocompatibility is an area of extensive debate. In this study, we have systematically investigated the effects of addition of low concentrations (0.01-0.2 wt. %) of 1-D and 2-D carbon nanomaterials (graphene oxide nanoplatelets, graphene oxide nanoribbons and carbon nanotubes) and inorganic nanomaterials (boron nitride nanotubes, boron nitride nanoplatelers, tungsten disulfide nanotubes and molybdenum disulfide nanoplatelets) on the mechanical properties, cytocompatibility, and bioactivity of poly(propylene fumarate) (PPF) nanocomposites towards their potential applications as porous and nonporous implants for bone tissue engineering. Addition of nanomaterials in the PPF matrix improved the compressive and flexural mechanical properties of non-porous crosslinked PPF nanocomposites and porous PPF scaffolds. Our results suggest that in addition to high surface roughness and surface area of the nanomaterials, the presence of functional groups on the surface of nanomaterials leads to an increased nanomaterial-polymer interaction and a uniform dispersion of nanomaterials in polymer matrix which may be the key factors responsible for an improved mechanical reinforcement. The in vitro studies showed an excellent cytocompatibility for both carbon and inorganic nanomaterial reinforced PPF nanocomposites and scaffolds. Protein adsorption studies and in vitro osteogenic differentiation studies also showed that addition of these 1-D and 2-D carbon and inorganic nanomaterials leads to an improved protein adsorption that promotes osteogenic differentiation and calcium mineralization in vitro. and good cytocompatibility of PPF nanocomposites. The long term implication of this research focuses on the development of mechanically strong, biocompatible, biodegradable and bioactive nanocomposites that can potentially replace commercial bone grafts that often lack the required mechanical properties for load bearing bone tissue engineering applications.

  4. Radiation-induced grafting of acrylic acid onto polypropylene film and its biodegradability

    NASA Astrophysics Data System (ADS)

    Mandal, Dev K.; Bhunia, Haripada; Bajpai, Pramod K.; Chaudhari, C. V.; Dubey, K. A.; Varshney, L.

    2016-06-01

    Polypropylene based commodity polyolefins are widely used in packaging, manufacturing, electrical, pharmaceutical and other applications. The aim of the present work is to study the effect of grafting of acrylic acid on the biodegradability of acrylic acid grafted polypropylene. The effect of different conditions showed that grafting percentage increased with increase in monomer concentration, radiation dose and inhibitor concentration but decreased with increase in radiation dose rate. The maximum grafting of 159.4% could be achieved at optimum conditions. The structure of grafted polypropylene films at different degree of grafting was characterized by EDS, FTIR, TGA, DSC, SEM and XRD. EDS studies showed that the increase in acrylic acid grafting percentage increased the hydrophilicity of the grafted films. FTIR studies indicated the presence of acrylic acid on the surface of polypropylene film. TGA studies revealed that thermal stability decreased with increase in grafting percentage. DSC studies showed that melting temperature and crystallinity of the grafted polypropylene films lower than polypropylene film. SEM studies indicated that increase in acrylic acid grafting percentage increased the wrinkles in the grafted films. The maximum biodegradability could be achieved to 6.85% for 90.5% grafting. This suggested that microorganisms present in the compost could biodegrade acrylic acid grafted polypropylene.

  5. Radiation chemistry of polymeric components of radioactive waste

    SciTech Connect

    Dziewinski, J. J.; Zagorski, Z.

    2002-01-01

    The presentation covers fragments of research on the role of radiation chemistry in radioactive waste management. Radioactive waste often contains polymeric materials contaminated with actinides, which exhibit a activity for thousands of years. Rules of safety of transportation and environmental security of permanent storage demand the understanding of radiation chemistry of typical waste matrices. Due to a slow decay and a short range of penetration of a emitters, the experiments with actinides are not easy. 'Therefore, accelerated experiments have been performed using 10 MeV electrons of high intensity. That way chemical effects proceeding over thousands of years could be reduced to minutes in the laboratory. Simulation of the effect of a-radiolysis on polymers by low LET radiation is justified, because low LET radiation produces multi-ionization spurs resulting in the same chemistry as high LET radiation.

  6. Development of hydrogels by radiation induced polymerization for use in slow drug delivery

    NASA Astrophysics Data System (ADS)

    Singh, Baljit; Bala, R.

    2014-10-01

    In the present work, in order to improve the drug release profile of indinavir sulfate, a potent inhibitor of HIV protease, controlled drug delivery systems in the form of hydrogels have been designed by a radiation graft polymerization method. These hydrogels have been prepared by using dietary fiber psyllium and binary monomers mixture of acrylamide (AAm) and 2-acrylamido-2-methylpropanesulfonic acid (AMPSA). These polymers have been characterized with cryo-SEMs, FTIR, XRD and swelling studies. The swelling of hydrogels has been determined in solution of different pH, temperature and [NaCl]. in vitro release studies of model drug indinavir sulfate in different pH have been carried out to determine the drug release mechanism. The release of dug occurred through non-Fickian mechanism.

  7. Enhancement of the grafting performance and of the water absorption of cassava starch graft copolymer by gamma radiation

    NASA Astrophysics Data System (ADS)

    Kiatkamjornwong, Suda; Meechai, Nispa

    1997-06-01

    Enhancement of the gamma radiation grafting of acrylonitrile onto gelatinized cassava starch was investigated. Infrared spectrometry was used to follow the chemical changes in the grafting reaction and from saponification. The saponified starch- g-PAN (HSPAN) was then characterized in terms of grafting parameters to provide a guide for the optimum total dose (kGy) and the appropriate ratio of starch/acrylonitrile for a fixed dose rate of 2.5 × 10 -1 kGy/min. Other dose rates were also carried out to obtain the appropriate result of grafting copolymerization and of water absorption. A thin aluminium foil, covering the inner wall of the reaction vessel, was found to be far more effective than any other metal films in the enhancement of the grafting reaction and the water absorption as well. Nitric acid in the medium increases the grafting yield and the water absorption. Methyl ether hydroquinone inhibitor was evaluated for its ability to increase homopolymerization and decrease graft reaction. When styrene was used as a comonomer, it hampered the grafting of acrylonitrile onto starch backbone. The water absorption capacity was improved by freeze-drying the HSPAN. The treatment of the HSPAN with aluminium trichloride hexahydrate was found to enhance the degree of wicking, but to decrease the water absorbency.

  8. Synthesis and characterization of N-vinylcaprolactam/N,N-dimethylacrylamide grafted onto chitosan networks by gamma radiation

    NASA Astrophysics Data System (ADS)

    Pérez-Calixto, M. P.; Ortega, A.; Garcia-Uriostegui, L.; Burillo, G.

    2016-02-01

    N-vinylcaprolactam (NVCL) and N,N-dimethylacrylamide (DMAAm) were grafted onto crosslinked chitosan by gamma radiation, using direct and indirect (pre-irradiation oxidative) methods. The binary graft systems were synthesized in one and two steps to evaluate the influences of architecture on the properties of the polymeric material. Maximum grafting percentages were obtained by the direct method. The different systems obtained were characterized by FTIR and TGA. The equilibrium swelling time of the (net-CS)-g-NVCL/DMAAm and [(net-CS)-g-NVCL]-g-DMAAm systems was 75 and 25 min, respectively, while crosslinked CS required about 24 h. Thermal and pH sensitivity were conserved in all systems; the pH response in [(net-CS)-g-NVCL]-g-DMAAm (LCST: 37°, pH: 5.2) is more defined than (net-CS)-g-NVCL/DMAAm (LCST: 37 °C, pH: 3.8). Grafting radiation showed to be an effective technique to modify CS hydrogels.

  9. UV-induced graft polymerization of acrylic acid in the sub-micronchannels of oxidized PET track-etched membrane

    NASA Astrophysics Data System (ADS)

    Korolkov, Ilya V.; Mashentseva, Anastassiya A.; Güven, Olgun; Taltenov, Abzal A.

    2015-12-01

    In this article, we report on functionalization of track-etched membrane based on poly(ethylene terephthalate) (PET TeMs) oxidized by advanced oxidation systems and by grafting of acrylic acid using photochemical initiation technique for the purpose of increasing functionality thus expanding its practical application. Among advanced oxidation processes (H2O2/UV) system had been chosen to introduce maximum concentration of carboxylic acid groups. Benzophenone (BP) photo-initiator was first immobilized on the surfaces of cylindrical pores which were later filled with aq. acrylic acid solution. UV-irradiation from both sides of PET TeMs has led to the formation of grafted poly(acrylic acid) (PAA) chains inside the membrane sub-micronchannels. Effect of oxygen-rich surface of PET TeMs on BP adsorption and subsequent process of photo-induced graft polymerization of acrylic acid (AA) were studied by ESR. The surface of oxidized and AA grafted PET TeMs was characterized by UV-vis, ATR-FTIR, XPS spectroscopies and by SEM.

  10. Obtention of injectable platelets rich-fibrin (i-PRF) and its polymerization with bone graft: technical note.

    PubMed

    Mourão, Carlos Fernando de Almeida Barros; Valiense, Helder; Melo, Elias Rodrigues; Mourão, Natália Belmock Mascarenhas Freitas; Maia, Mônica Diuana-Calasans

    2015-12-01

    The use of autologous platelet concentrates, represent a promising and innovator tools in the medicine and dentistry today. The goal is to accelerate hard and soft tissue healing. Among them, the platelet-rich plasma (PRP) is the main alternative for use in liquid form (injectable). These injectable form ofplatelet concentrates are often used in regenerative procedures and demonstrate good results. The aim of this study is to present an alternative to these platelet concentrates using the platelet-rich fibrin in liquid form (injectable) and its use with particulated bone graft materials in the polymerized form. PMID:26814997

  11. Functionalization of cotton fabrics by radiation induced grafting of quaternary salt to impart antibacterial property

    NASA Astrophysics Data System (ADS)

    Goel, N. K.; Kumar, Virendra; Rao, M. S.; Bhardwaj, Y. K.; Sabharwal, S.

    2011-11-01

    High energy gamma radiation has been used to covalently link polymer chains of a quaternary ammonium salt containing monomer, viz. [2-(Acryloyloxyethyl)]trimethylammonium chloride (AETC) to cotton fabric by mutual radiation grafting using 2-hydroxyethyl methacrylate (2-HEMA) monomer as the grafting facilitator. Grafting yield was found to increase with the radiation dose and monomer concentration. The grafted samples have been characterized for water uptake, surface morphology and thermal stability and for their antibacterial efficacy against various bacteria and were found to possess significant antibacterial activity particularly against gram-positive bacteria.

  12. Radiation-grafted, chemically modified membranes part I - Synthesis of a selective aluminum material

    NASA Astrophysics Data System (ADS)

    Bazante-Yamaguishi, Renata; Moura, Eduardo; Manzoli, José E.; Geraldo, Aurea B. C.

    2014-01-01

    Polymeric membranes were styrene grafted by irradiation methods and the obtained material was chemically modified to become aluminum selective. For this purpose, polymeric substrates of PVC (polyvinyl chloride) and PP (polypropylene) were styrene grafted mutually by gamma and electron beam irradiation. The modification process includes three basic reaction paths: Friedel-Crafts acylation, 2-methylanisole coupling and a final oxidation to achieve aluminum selectivity. Although this specific chemical modification in derivatives of polystyrene is not new, the new challenge is to obtain a selective material where original membrane characteristics (physical shape and mechanical resistance) are minimally conserved after such an aggressive treatment.

  13. Thermo-responsive wound dressings by grafting chitosan and poly(N-isopropylacrylamide) to plasma-induced graft polymerization modified non-woven fabrics

    NASA Astrophysics Data System (ADS)

    Chen, Jyh-Ping; Kuo, Chang-Yi; Lee, Wen-Li

    2012-12-01

    To obtain a chitosan wound dressings with temperature-responsive characteristics, polypropylene (PP) non-woven fabric (NWF) was modified by direct current pulsed oxygen plasma-induced grafting polymerization of acrylic acid (AAc) to improve hydrophilicity and to introduce carboxylic acid groups. Conjugation of chitosan and poly(N-isopropylacrylamide) (PNIPAAm) followed by using water-soluble carbodiimide as a coupling agent to form a novel bigraft PP-g-chitosan-g-PNIPAAm wound dressing. The amount of chitosan and PNIPAAm grafted to PP-g-chitosan-g-PNIPAAm were 83.0 ± 4.6 μg/cm2 and 189.5 ± 8.2 μg/cm2, respectively. The surface chemical composition and microstructure of the NWF were studied by electron spectroscopy for chemical analysis (ESCA) and scanning electron microscopy (SEM). The linkages between AAc, chitosan, and PNIPAAm were confirmed with the formation of amide bonds. Physical properties of the NWF were characterized and potentials of these NWFs as wound dressings were evaluated using SD rat as the animal model. NWFs contained PNIPAAm were better than those contained only chitosan in wound healing rates and the wound areas covered by PP-g-chitosan-g-PNIPAAm wound dressings healed completely in 17 days.

  14. A novel polymeric flocculant based on polyacrylamide grafted inulin: aqueous microwave assisted synthesis.

    PubMed

    Rahul, Rahul; Jha, Usha; Sen, Gautam; Mishra, Sumit

    2014-01-01

    Polyacrylamide grafted inulin (In-g-PAM) was synthesized via aqueous microwave assisted method (using ceric ammonium nitrate in synergism with microwave in aqueous medium). The intended grafting of the PAM chains on polysaccharide backbone was confirmed through standard physicochemical characterization techniques, namely intrinsic viscosity measurement, Fourier transform infrared (FTIR) spectroscopy, elemental analysis (C, H, N and O), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) studies. Flocculation efficacy of various grades of synthesized grafted product was studied in coal fines suspension, in relation to inulin (parent polysaccharide). This was done utilizing jar test and settling test procedure, towards possible application as a flocculant for coal washery effluents. PMID:24274474

  15. Generation of functional coatings on hydrophobic surfaces through deposition of denatured proteins followed by grafting from polymerization.

    PubMed

    Goli, Kiran K; Rojas, Orlando J; Ozçam, A Evren; Genzer, Jan

    2012-05-14

    Hydrophilic coatings were produced on flat hydrophobic substrates featuring n-octadecyltrichlorosilane (ODTS) and synthetic polypropylene (PP) nonwoven surfaces through the adsorption of denatured proteins. Specifically, physisorption from aqueous solutions of α-lactalbumin, lysozyme, fibrinogen, and two soy globulin proteins (glycinin and β-conglycinin) after chemical (urea) and thermal denaturation endowed the hydrophobic surfaces with amino and hydroxyl functionalities, yielding enhanced wettability. Proteins adsorbed strongly onto ODTS and PP through nonspecific interactions. The thickness of adsorbed heat-denatured proteins was adjusted by varying the pH, protein concentration in solution, and adsorption time. In addition, the stability of the immobilized protein layer was improved significantly after interfacial cross-linking with glutaraldehyde in the presence of sodium borohydride. The amino and hydroxyl groups present on the protein-modified surfaces served as reactive sites for the attachment of polymerization initiators from which polymer brushes were grown by surface-initiated atom-transfer radical polymerization of 2-hydroxyethyl methacrylate. Protein denaturation and adsorption as well as the grafting of polymeric brushes were characterized by circular dichroism, ellipsometry, contact angle, and Fourier transform infrared spectroscopy in the attenuated total reflection mode. PMID:22414148

  16. Radiation-induced grafting of vinylbenzyl chloride onto a poly(ether ether ketone) film

    NASA Astrophysics Data System (ADS)

    Hwang, Mi-Lim; Song, Ju-Myung; Ko, Beom-Seok; Sohn, Joon-Yong; Nho, Young-Chang; Shin, Junhwa

    2012-06-01

    In this study, the effects of various irradiation conditions including solvent, monomer concentration, total dose, and dose rate on the radiation grafting of a VBC monomer onto a PEEK aromatic hydrocarbon film for the preparation of a PVBC-grafted PEEK (PEEK-g-PVBC) film were investigated. The results show that the desired PVBC-grafted PEEK film can be prepared using a simultaneous irradiation grafting method, and that the degree of grafting (DOG) of the film is largely influenced by the irradiation conditions. Among the applied solvents, halogenated solvents, dichloromethane and chloroform, were found to be suitable for grafting. The successful preparation of the grafted film was confirmed using analytical instruments such as FT-IR, TGA, and SEM-EDX.

  17. Radiation-grafting of acrylamide onto silicone rubber films for diclofenac delivery

    NASA Astrophysics Data System (ADS)

    Magaña, Hector; Palomino, Kenia; Cornejo-Bravo, Jose M.; Alvarez-Lorenzo, Carmen; Concheiro, Angel; Bucio, Emilio

    2015-02-01

    This work focuses on the pre-irradiation grafting of acrylamide (AAm) onto silicone rubber films (SR) and evaluates the effect of gamma-ray radiation conditions on the grafting yield, which in turn may influence the performance of the grafted materials as components of drug-eluting devices. Pristine and modified SR were characterized using FTIR-ATR, DSC, TGA, swelling, and water contact angle analysis in order to elucidate the effects of AAm grafting onto SR. Grafted films with content in AAm ranging from 0.81% to 22.20% showed excellent cytocompatibility against fibroblasts, and capability to uptake the anti-inflammatory drug diclofenac. Amount of drug loaded directly correlated with the grafting degree of the films. Drug release studies were performed at pH 7.4 and 37 °C (physiological conditions). Most grafted films released the drug in a sustained way for at least three hours.

  18. Transparent Metal-Salt-Filled Polymeric Radiation Shields

    NASA Technical Reports Server (NTRS)

    Edwards, David; Lennhoff, John; Harris, George

    2003-01-01

    "COR-RA" (colorless atomic oxygen resistant -- radiation shield) is the name of a transparent polymeric material filled with x-ray-absorbing salts of lead, bismuth, cesium, and thorium. COR-RA is suitable for use in shielding personnel against bremsstrahlung radiation from electron-beam welding and industrial and medical x-ray equipment. In comparison with lead-foil and leaded-glass shields that give equivalent protection against x-rays (see table), COR-RA shields are mechanically more durable. COR-RA absorbs not only x-rays but also neutrons and rays without adverse effects on optical or mechanical performance. The formulation of COR-RA with the most favorable mechanical-durability and optical properties contains 22 weight percent of bismuth to absorb x-rays, plus 45 atomic percent hydrogen for shielding against neutrons.

  19. Characterization of methyl methacrylate grafting onto preirradiated biodegradable lignocellulose fiber by gamma-radiation.

    PubMed

    Khan, Ferdous

    2005-01-14

    Gamma-radiation-induced graft copolymerization of methyl methacrylate onto natural lignocellulose (jute) fiber was carried out by the preirradiation method in an aqueous medium by using octylphenoxy-polyethoxyethanol as an emulsifier. The different factors that influenced the graft copolymer reaction process were investigated. In the case of radiation-dose-dependent grafting, samples irradiated in the presence of air produced up to 73% graft weight compared to 53% obtained in the case of irradiation in a nitrogen environment. By assuming Arrhenius reaction kinetics, the activation energy (E(a)) of the grafting reaction process was evaluated for different reaction temperatures. Moreover, the graft copolymer reaction was controlled by incorporating a homopolymer-inhibiting agent and three different chain-transfer agents in the reaction medium. The mechanical and thermal properties of jute fiber 'as received' and jute-graft-poly(methyl methacrylate) were also investigated. The results showed that the percentage of grafting with jute fiber has a significant effect on the properties. The kinetic parameters were evaluated from TGA thermograms by using Broido's method in the temperature range 240-350 degrees C. Scanning electron micrographs show that the structural changes on the surface of jute fibers were induced by graft copolymerization of methyl methacrylate monomer. Fiber-fiber surface friction was measured in terms of the average maximum load and the kinetic friction. SEM of jute-graft-poly(methyl methacrylate). PMID:15635719

  20. Controlled polymerization chemistry to graft architectures that influence cell-material interactions.

    PubMed

    Sebra, Robert P; Reddy, Sirish K; Masters, Kristyn S; Bowman, Christopher N; Anseth, Kristi S

    2007-03-01

    Acrylate monomers were photografted from polymer substrates to create cell responsive chemically and biologically active surfaces that manipulate cell response. Three monomers, polyethylene glycol monoacrylate (MW 375 g/mol) (PEG375A), a monomeric extra-cellular matrix protein, and a cell-cleavable fluorescent monomer, were spatially photopatterned from a base substrate. The base substrate consisted of a dithiocarbamate (DTC) functionalized urethane diacrylate/tri(ethylene glycol)diacrylate copolymer and was shown to non-specifically support NIH 3T3 fibroblast cell adhesion. The DTC-containing polymer was further modified by grafting PEG375A to demonstrate selective blocking of cell-material interactions. Next, acrylated collagen type I was patterned onto polymer substrates to further promote specific cell interactions (i.e. by presenting cell-adhesive moieties). Hydrophilic PEG375A grafted patterns were shown to prevent 3T3 fibroblast adhesion to polymer in spatially grafted regions, while biologically active acrylated collagen type I promoted cell-surface interactions. Collagen type I was grafted at varying densities (0-7.5 pmol/grafted square), and the extent of cell adhesion and spreading were evaluated for each of these graft densities using fluorescence microscopy. Finally, methacrylated carboxyfluorescein diacetate (CFDA) was synthesized and photografted onto a cell-adhesive substrate as a cell sensing mechanism. The acetate groups found in the structure of CFDA cleave in the presence of cells. This cell-responsive substrate results in fluorescence indicative of acetate-group cleavage associated with cell interactions that occurs in patterned regions on polymer surfaces. Collectively, the results herein show the utility and application of a spatially and temporally controlled photografting process for designing cell responsive polymer surfaces. PMID:17236829

  1. Construction of stable polymeric vesicles based on azobenzene and beta-cyclodextrin grafted poly(glycerol methacrylate)s for potential applications in colon-specific drug delivery.

    PubMed

    Gu, Wen-Xing; Li, Qing-Lan; Lu, Hongguang; Fang, Lei; Chen, Qixian; Yang, Ying-Wei; Gao, Hui

    2015-03-18

    Polymeric vesicles constructed from cyclodextrin- and azobenzene-grafted poly(glycidyl methacrylate)s showed excellent stability owing to the multiple host-guest complexation. Upon culturing in Na2S2O4-contained buffer solution, cargo-loaded vesicles disassembled, for potential applications in colon-specific drug delivery. PMID:25692460

  2. Modification of polyetherurethane for biomedical application by radiation induced grafting. II. Water sorption, surface properties, and protein adsorption of grafted films.

    PubMed

    Jansen, B; Ellinghorst, G

    1984-01-01

    A series of polyetherurethane films grafted by means of gamma radiation with hydrophilic or reactive monomers (2-hydroxyethyl methacrylate, 2,3-epoxypropyl methacrylate, 2,3-dihydroxypropyl methacrylate, and acrylamide) and partially chemically modified were subjected to various physico-chemical investigation methods involving water sorption, contact angle, and protein adsorption measurements. From contact angle data the interfacial free energy gamma sw between grafted films and water was calculated. It was found that the water uptake of grafted films increases with grafting yield or, in the case of grafted and afterwards chemically modified films, with reaction yield; the diffusion coefficient of water in the modified films also increases with grafting yield. Contact angle studies revealed all grafted films to have surfaces more hydrophilic than the ungrafted trunk polymer. The degree of hydrophilicity--especially of HEMA-grafted films--strongly depends on grafting conditions. For some grafted samples with high surface hydrophilicity very low interfacial free energies approaching zero were measured. The study of the competitive adsorption of bovine serum albumin, gamma-globulin, and fibrinogen from a synthetic protein solution onto modified films showed that the adsorption of albumin increases markedly with increasing grafting yields, whereas the fibrinogen and gamma-globulin adsorption only slightly increases. A correlation between interfacial free energy and protein adsorption in the sense of the "minimum interfacial free energy hypothesis" was found only for samples with grafting yields below 5%. At higher grafting yields the increased surface area complicates the analysis. PMID:6085798

  3. Radical graft polymerization of an Allyl Monomer onto Hydrophilic Polymers and their antibacterial nanofibrous membranes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Hydrophilic poly (vinyl alcohol-co-ethylene) (PVA-co-PE) copolymers with 27 mol %, 32 mol % and 44 mol % ethylene were functionalized by melt radical graft copolymerization with 2,4-diamino-6-diallylamino-1,3,5-triazine (NDAM) using reactive extrusion. This functionalization imparts antibacterial pr...

  4. Immobilization of enzymes and antibodies to radiation grafted polymers for therapeutic and diagnostic applications

    NASA Astrophysics Data System (ADS)

    Hoffman, Allan S.; Gombotz, Wayne R.; Uenoyama, Satoshi; Dong, Liang C.; Schmer, Gottfried

    Pre-irradiation and mutual radiation grafting were employed to produce poly(methacrylic acid) (MAAc) hydrogels on polypropylene/polyethylene (PP/PE) copolymer films, PP films and porous PP fibers of a plasma filter. A diphenyl picryl hydrazyl (DPPH) assay was developed to measure the surface peroxide concentration of the pre-irradiated PP/PE films prior to grafting. Mutually grafted porous PP fibers were used for subsequent immobilization of L-asparaginase while the mutually grafted PP/PE films were used to immobilize a schistosoma monoclonal antibody.

  5. Stearyl methacrylate-grafted-chitosan nanoparticle as a nanofiller for PLA: Radiation-induced grafting and characterization

    NASA Astrophysics Data System (ADS)

    Rattanawongwiboon, Thitirat; Haema, Kamonwon; Pasanphan, Wanvimol

    2014-01-01

    This paper reports a one-pot synthesis using radiation-induced grafting technique to modify biopolymer-based chitosan nanoparticles as a nanofiller for blending with poly(lactic acid) (PLA). Hydrophobic stearyl methacrylate (SMA) was grafted onto non-irradiated chitosan (CS0) and pre-irradiated chitosan with a γ-ray dose of 40 kGy (CS40) to obtain stearyl methacrylate-grafted-chitosan nanoparticles (SMA-g-CSNPs).The effects of the pre-irradiated CS, grafting doses and SMA concentrations on degree of grafting (DG) and particle formation were studied. FT-IR and XRD were used to characterize the chemical and packing structure of SMA-g-CSNPs. The particle formulation and size of SMA-g-CSNPs were observed by TEM and AFM. The spherical core-shell SMA-g-CSNPs with the size ranging from 50 to 140 nm were successfully prepared. The SMA-g-CSNPs from CS40 has higher DG and smaller particle size when compared with CS0. The SMA-g-CSNPs are able to improve the compatibility between CS and PLA.

  6. Radiation-induced graft copolymerization of hydrophilic monomers onto polyphosphazenes

    NASA Astrophysics Data System (ADS)

    Lora, S.; Carenza, M.; Palma, G.; Caliceti, P.

    Grafting of N-vinyl-2-pyrrolidone onto poly|(trifluoroethoxy)phosphazenel and poly |bis (phenoxy)phosphazenel | films was carried out by direct irradiation at 0.5 Gy/s and 20°C, using different monomer/methanol mixtures. The grafting reaction kinetics was followed. The improvement of biocompatibility produced by grafting N-vinyl-2-pyrrolidone onto the two polyphosphazenes was evaluated by means of "in vivo" tests.

  7. Radiation-induced polymerization for the immobilization of penicillin acylase

    SciTech Connect

    Boccu, E.; Carenza, M.; Lora, S.; Palma, G.; Veronese, F.M.

    1987-06-01

    The immobilization of Escherichia coli penicillin acylase was investigated by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperature. A leak-proof composite that does not swell in water was obtained by adding the cross-linking agent trimethylolpropane trimethacrylate to the monomer-aqueous enzyme mixture. Penicillin acylase, which was immobilized with greater than 70% yield, possessed a higher Km value toward the substrate 6-nitro-3-phenylacetamidobenzoic acid than the free enzyme form (Km = 1.7 X 10(-5) and 1 X 10(-5) M, respectively). The structural stability of immobilized penicillin acylase, as assessed by heat, guanidinium chloride, and pH denaturation profiles, was very similar to that of the free-enzyme form, thus suggesting that penicillin acylase was entrapped in its native state into aqueous free spaces of the polymer matrix.

  8. Biodegradability of poly(3-hydroxybutyrate) film grafted with vinyl acetate: Effect of grafting and saponification

    NASA Astrophysics Data System (ADS)

    Wada, Yuki; Seko, Noriaki; Nagasawa, Naotsugu; Tamada, Masao; Kasuya, Ken-ichi; Mitomo, Hiroshi

    2007-06-01

    Radiation-induced graft polymerization of vinyl acetate (VAc) onto poly(3-hydroxybutyrate) (PHB) film was carried out. At a degree of grafting higher than 5%, the grafted films (PHB-g-VAc) completely lost the enzymatic degradability that is characteristic of PHB due to the grafted VAc covering the surface of the PHB film. However, the biodegradability of the PHB-g-VAc films was recovered when the films were saponified in alkali solution under optimum conditions. Graft chains of the PHB-g-VAc film reacted selectively to become biodegradable polyvinyl alcohol (PVA). The biodegradability of the saponified PHB-g-VAc film increased rapidly with time.

  9. Influence of gamma radiation onto polymeric matrix with papain

    NASA Astrophysics Data System (ADS)

    Zulli, Gislaine; Lopes, Patrícia Santos; Velasco, Maria Valéria Robles; Alcântara, Mara Tânia Silva; Rogero, Sizue Ota; Lugao, Ademar Benévolo; Mathor, Monica Beatriz

    2010-03-01

    Papain is a proteolytic enzyme that has been widely used as debridement agent for scars and wound healing treatment. However, papain presents low stability, which limits its use to extemporaneous or short shelf-life formulations. The purpose of this study was to entrap papain into a polymeric matrix in order to obtain a drug delivery system that could be used as medical device. Since these systems must be sterile, gamma radiation is an interesting option and presents advantages in relation to conventional agents: no radioactive residues are formed; the product can be sterilized inside the final packaging and has an excellent reliability. The normative reference for the establishment of the sterilizing dose determines 25 kGy as the inactivation dose for viable microorganisms. A silicone dispersion was selected to prepare membranes containing 2% (w/w) papain. Irradiated and non-irradiated membranes were simultaneously assessed in order to verify whether gamma radiation interferes with the drug-releasing profile. Results showed that irradiation does not affect significantly papain release and its activity. Therefore papain shows radioresistance in the irradiation conditions applied. In conclusion, gamma radiation can be easily used as sterilizing agent without affecting the papain release profile and its activity onto the biocompatible device is studied.

  10. Polymeric Prodrug Grafted Hollow Mesoporous Silica Nanoparticles Encapsulating Near-Infrared Absorbing Dye for Potent Combined Photothermal-Chemotherapy.

    PubMed

    Zhang, Yuanyuan; Ang, Chung Yen; Li, Menghuan; Tan, Si Yu; Qu, Qiuyu; Zhao, Yanli

    2016-03-23

    In this study, polymeric prodrug coated hollow mesoporous silica nanoparticles (HMSNs) with encapsulated near-infrared (NIR) absorbing dye were prepared and explored for combined photothermal-chemotherapy. A copolymer integrated with tert-butoxycarbonyl protected hydrazide groups and oligoethylene glycols was initially grafted on the surface of HMSNs via reversible addition-fragmentation chain-transfer (RAFT) polymerization followed by the deprotection to reactivate the hydrazide groups for the conjugation of anticancer drug doxorubicin (DOX). DOX was covalently bound onto the polymer substrate by acid-labile hydrazone bond and released quickly in weak acidic environment for chemotherapy. The hollow cavity of HMSNs was loaded with an NIR absorbing dye IR825 to form the final multifunctional hybrid denoted as HMSNs-DOX/IR825. The hybrid exhibited good dispersity and stability as well as high light-to-heat conversion efficiency. As revealed by confocal microscopy and flow cytometry analysis, the hybrid was efficiently taken up by cancer cells, and the conjugated DOX could be released under the cellular environment. In vitro cytotoxicity study demonstrated that anticancer activity of HMSNs-DOX/IR825 could be significantly improved by the NIR irradiation, which led to a satisfactory therapeutic efficacy through the combination treatment. Thus, the developed hybrid could be a promising candidate for the combined photothermal-chemotherapy of cancer. PMID:26937591

  11. Preparation of poly( N-isopropylacrylamide) brush grafted silica particles via surface-initiated atom transfer radical polymerization used for aqueous chromatography

    NASA Astrophysics Data System (ADS)

    Liu, Zong-Jian; Liang, Yan-Li; Geng, Fang-Fang; Lv, Fang; Dai, Rong-Ji; Zhang, Yu-Kui; Deng, Yu-Lin

    2012-03-01

    Thermoresponsive poly( N-isopropylacrylamide) (PNIPAAm) brushes were densely grafted onto silica surface via surface-initiated atom transfer radical polymerization (SI-ATRP). The grafting reaction started from the surfaces of 2-bromoisobutyratefunctionalized silica particles in 2-propanol aqueous solution at ambient temperature using CuCl/CuCl2/ N,N,N',N',N″-pentamethyldiethylenetriamine (PMDETA) as the catalytic system. Based on thermogravimetric analysis (TGA) results, the grafting amount and grafting density of PNIPAM chains on the surface of silica were calculated to be 1.29 mg/ m2 and 0.0215 chains/nm2, respectively. The gel permeation chromatography (GPC) result showed the relatively narrow molecular weight distribution ( M w/ M n= 1.21) of the grafted PNIPAAm. The modified silica particles were applied as high-performance liquid chromatography (HPLC) packing materials to successfully separate three aromatic compounds using water as mobile phase by changing column temperature. Temperature-dependent hydrophilic/hydrophobic property alteration of PNIPAAm brushes grafted on silica particles was determined with chromatographic interaction between stationary phase and analytes. Retention time was prolonged and resolution was improved with increasing temperature. Baseline separation with high resolution at relatively low temperatures was observed, demonstrating dense PNIPAAm brushes were grafted on silica surfaces.

  12. Synthesis and Characterization of Surface Grafted Poly(N-isopropylacrylamide) and Poly(Carboxylic Acid)– Iron Particles via Atom Transfer Radical Polymerization for Biomedical Applications

    PubMed Central

    Sutrisno, Joko; Fuchs, Alan; Evrensel, Cahit

    2014-01-01

    This research relates to the preparation and characterization of surface grafted poly(N-isopropylacrylamide) and poly(carboxylic acid)–micron-size iron particles via atom transfer radical polymerization (ATRP). The surface grafted polymers–iron particles result in multifunctional materials which can be used in biomedical applications. The functionalities consist of cell targeting, imaging, drug delivery, and immunological response. The multifunctional materials are synthesized in two steps. First, surface grafting is used to place polymer molecules on the iron particles surface. The second step, is conjugation of the bio-molecules onto the polymer backbone. Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy were used to confirm the presence of polymers on the iron particles. The thickness of the grafted polymers and glass transition temperature of the surface grafted polymers were determined by transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The covalent bond between grafted polymers and iron particles caused higher glass transition temperature as compared with non-grafted polymers. The ability to target the bio-molecule and provide fluorescent imaging was simulated by conjugation of rat immunoglobulin and fluorescein isothiocyanate (FITC) labeled anti-rat. The fluorescence intensity was determined using flow cytometry and conjugated IgG-FITC anti-rat on iron particles which was imaged using a fluorescence microscopy. PMID:25382869

  13. Surface-initiated Ring-opening Metathesis Polymerization in the Vapor Phase: An Efficient Method for Grafting Cyclic Olefins of Low Strain Energies

    PubMed Central

    Lerum, Maria Felisa Z.; Chen, Wei

    2011-01-01

    Surface grafting of cyclic olefins with low strain energies, including cyclopentene (CP), 1,4-cyclohexadiene (CHD), cycloheptene (CHP), cis-cyclooctene (CO), cis,cis-1,5-cyclooctadiene (COD), 1,3,5,7-cyclooctatetraene (COT), cyclododecene (CD), and trans,trans,cis-1,5,9-cyclododecatriene (CDT), were explored using ring-opening metathesis polymerization in the vapor phase. These monomers do not polymerize when SiROMP is carried out in solution due to pronounced chain transfer on surfaces where chains are in close proximities. In the vapor phase, however, chain transfer is suppressed at the solid-vapor interfaces, which permits the polymerization of most of these monomers. A minimal required strain energy of 2.2 kcal/mol was determined in this study, which is significantly lower than the estimated 13.3 kcal/mol for SiROMP carried out in solution, indicating that the enhancement in monomer polymerizability is significant using the vapor phase approach. A series of polyalkenamers with controlled fraction of unsaturation from 8% to 50% along the polymer backbone were grafted to solid substrates. It was observed that the logarithm of largest grafted layer thickness obtained before the removal of chain transfer products – which correlates with the extent of polymerization – scales with monomer strain energy. This confirms that the release of ring strain is the thermodynamic driving force for SiROMP. It was also found that although chain transfer is suppressed in the vapor phase, it is important in monomer/polymer systems where the fraction of unsaturated bonds is high. In these cases, grafted polymer thickness is dominated by chain transfer, rather than by monomer strain energy. A quantitative relationship is established for estimating graft thickness of a particular monomer using its strain energy and fraction of unsaturated bonds in the monomer. PMID:21469729

  14. Grafted α-hydroxyphosphonic acids onto polymeric supports: preparation, characterization, and antimicrobial effect.

    PubMed

    Nichita, Ileana; Popa, Adriana; Dragan, Ecaterina Stela; Iliescu, Smaranda; Ilia, Gheorghe

    2015-01-01

    The paper deals with the preparation and characterization of compounds with antimicrobial activity: α-hydroxyphosphonic acids grafted onto styrene-12%-(15%)-divinylbenzene copolymer. These products proved to have antimicrobial effect against two species of gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and two species of gram-positive bacteria (Staphylococcus aureus and Bacillus cereus) and a species of yeast (Candida albicans). Tests showed the reduction of bacterial load at different time intervals during the 18 h of contact. PMID:25789417

  15. Crystal structure and mechanical properties of UHMWPE-g-PMA fiber prepared by radiation grafting

    NASA Astrophysics Data System (ADS)

    Xing, Zhe; Wang, Mouhua; liu, Weihua; Hu, Jiangtao; Wu, Guozhong

    2013-05-01

    Methyl acrylate (MA) monomer was grafted onto ultra-high molecular weight polyethylene (UHMWPE) fibers by γ-ray pre-irradiation induced graft polymerization. The grafting of MA on UHMWPE fiber was confirmed by thermogravimetric analysis and Fourier-transform infrared spectroscopy. The degree of grafting (DG) increased with an increase in absorbed dose and reached a significantly high value (approximately 200%) at 100 kGy. Scanning electron microscopy analysis revealed that the surface of the UHMWPE-g-PMA fibers was covered by the MA grafting layer and became rough. The monoclinic crystalline and orientated intermediate phases were disordered by the grafting chains such that degree of orientation declined gradually with increasing DG. The tensile strength of UHMWPE-g-PMA fiber decreased with increasing dose but was independent of DG, whereas the fiber modulus declined with DG. UHMWPE-g-PMA fiber that possesses desirable mechanical properties could be obtained at a dose of less than 10 kGy.

  16. Polymer-grafted silica: A screening system for polymeric adsorption resin development

    SciTech Connect

    Browne, T.E.; Cohen, Y. )

    1993-04-01

    A screening-level methodology was developed for the evaluation of solute affinity for polymers that are candidate sorption resins. In this approach novel grafted polymer-silica resins were synthesized to produce poly(vinylpyrrolidone)-silica (PVP-Si) and poly(vinyl acetate)-silica (PVAc-Si) resins. The polymer-silica resins along with a number of commercially available polymer resins were used to evaluate the aqueous-phase adsorption of phenol, tetrachloroethene (PCE), trichloroethene (TCE), and chloroform. The polymer-grafted silicas were able to selectively remove pollutants from water with a covalently bonded polymer layer that has a high affinity for the target pollutant. The PVAc-silica resin had a sorption capacity for TCE and CHCl[sub 3] as high as commercial poly(styrene) resin XAD-4; the PVP-Si resin had a sorption capacity for phenol higher than a commercial poly-(vinylpyridine) resin (Reillex 425). PCE adsorption onto the PVAc-silica was comparable to the commercial poly(methacrylate) and poly(vinylpyridine) resins but less than the poly(styrene) resin. The results show that the Hildebrand solubility parameter along with the dipole moment of the polymer functional groups can be used for an initial screening-level assessment of polymer-solute affinity.

  17. Synthesis, modification and graft polymerization of magnetic nano particles for PAH removal in contaminated water

    PubMed Central

    2014-01-01

    Magnetic nanoparticles (MNPs) were modified with 3-Mercaptopropytrimethoxysiline (MPTMS) and grafted with allyl glycidyl ether for coupling with beta naphtol as a method to form a novel nano-adsorbent to remove two poly aromatic hydrocarbons (PAHs) from contaminated water. The modified MNPs were characterized by transmission electron microscopy, infrared spectroscopy and thermogravimetric analysis. Results showed that the modified MNPs enhanced the process of adsorption. Tests were done on the adsorption capacity of the two PAHs on grafted MNPs; factors applied to the tests were temperature, contact time, pH, salinity and initial concentration of PAHs. Results revealed that adsorption equilibrium was achieved in 10 min, and the maximum adsorption capacity was determined as 4.15 mg/g at pH = 7.0 and 20°C. The equilibrium adsorption data of the two PAHs by the modified MNPs were analyzed by Langmuir, Freundlich and Temkin models. Equilibrium adsorption data was determined from the Langmuir, Freundlich and Temkin constants from tests under conditions of pH = 7 and temperature 20°C. Analysis of the adsorption-desorption process indicated that the modified MNPs had a high level of stability and good reusability. Magnetic separation in these tests was fast and this shows that the modified MNPs have great potential to be used as a new adsorbent for the two PAHs removal from contaminated water in water treatment. PMID:25101170

  18. Ion-containing reverse osmosis membranes obtained by radiation grafting method

    NASA Astrophysics Data System (ADS)

    Hegazy, El-Sayed A.; El-Assy, Nasef B.; Dessouki, Ahmed M.; Shaker, Manal M.

    Cationic membranes obtained by radiation grafting of acqueous acrylic acid onto low density polyethylene films followed by alkaline treatment to confer ionic character in the graft chains, were tested for reverse osmosis desalination of saline water. Selected physical properties of such membranes were investigated. The grafted membranes prossess good mechanical and electrical properties. Water uptake for the alkali-treated membrane was much higher than that of the alkali-untreated one. The effect of operation time, degree of grafting, applied pressure and feed concentration on the water flux and salt rejection for the grafted membranes was investigated. Such cationic membranes showed good durability, thermal and chemical stability, acceptable water flux and salt rejection which may make them acceptable for practical use in reverse osmosis desalination of sea water.

  19. Mucoadhesive thermo-responsive chitosan-g-poly(N-isopropylacrylamide) polymeric micelles via a one-pot gamma-radiation-assisted pathway.

    PubMed

    Sosnik, Alejandro; Imperiale, Julieta C; Vázquez-González, Brenda; Raskin, Maya Menaker; Muñoz-Muñoz, Franklin; Burillo, Guillermina; Cedillo, Gerardo; Bucio, Emilio

    2015-12-01

    Thermo-sensitive graft copolymer amphiphiles of chitosan (CS) and poly(N-isopropylacrylamide) (PNiPAAm), CS-g-PNIPAAm, were successfully synthesized by a catalyst-less one-pot gamma (γ)-radiation-assisted free radical polymerization at three different radiation doses: 5, 10 and 20 kGy. The chemical structure of the copolymers was confirmed by FTIR and solid-state (13)C NMR and the grafting extent by (1)H NMR and gravimetric analysis. In general, the higher the dose, the smaller the grafting due to the more significant NiPAAm homopolymerization. Due to the grafting of poly(NiPAAm) blocks, aqueous solutions of the different copolymers underwent a sharp transition upon heating above 32 °C, the characteristic lower critical solution temperature (LCST) of poly(NiPAAm). Then, the critical micellar concentration (CMC), the size and size distribution and the zeta-potential were characterized by dynamic light scattering (DLS) and the polymeric micelles visualized in suspension and quantified by Nanoparticle Tracking Analysis (NTA), at 37 °C. CMC values were in the 0.0012-0.0025%w/v range and micelles displayed sizes between 99 and 203 nm with low polydispersity (<0.160) and highly positive zeta-potential (>+15 mV) that suggested the partial conservation of the amine groups upon NiPAAm grafting. Consequently, polymeric micelles displayed the intrinsic mucoadhesiveness of CS, as established in vitro by the mucin solution assay. Finally, the encapsulation capacity of the micelles was assessed with the highly hydrophobic protease inhibitor antiretroviral indinavir free base (IDV). Polymeric micelles led to a significant 24-fold increase of the aqueous solubility from 63 μg/mL to 1.45 mg/mL, a performance remarkably better than different poly(ethylene oxide)-b-poly(propylene oxide) block copolymers assessed before. Overall results highlight the potential of this nanotechnology platform to expand the application of polymeric micelles to mucosal administration routes. PMID:26551867

  20. Bioresponse to polymeric substrates: Effect of surface energy, modulus, topography, and surface graft copolymers

    NASA Astrophysics Data System (ADS)

    Wilson, Leslie Hoipkemeier

    Biofouling is the accumulation of biological matter on a substrate. It is essential to elucidate and model the major factors that affect both biological settlement and adhesion to substrates in order to develop coatings that minimize initial fouling or ease the removal of this fouling. To date, models that have estimated adhesion strength to coatings primarily included bulk elastic modulus and surface energy. Topography, however, has been found to dominate both these terms in the reduction of settlement and has been found to affect the adhesion strength as well. Silicone foul release coatings have demonstrated moderate success in the prevention of marine biofouling because of their low modulus and low surface energy. Problems exist with durability and eventual fouling of the coating due to the overgrowth of foulants that prefer hydrophobic substrates. This research details the characterization and the surface and bulk modification of a commercially available silicone elastomer. The modifications include bulk additives, surface topography, and surface graft copolymers. The effect of these modifications on biological response was then assayed using the alga Ulva as a model for marine biofouling. The unmodified silicone elastomer has a bulk modulus of approximately 1 MPa. The addition of vinyl functional polydimethylsiloxane oils allowed for a greater than 200% increase or a 90% decrease in the bulk modulus of the material. The addition of non-reactive polydimethylsiloxane oils allowed for a change in the surface lubricity of the elastomer without a significant change in the mechanical properties. Topographical modifications of the surface show a profound effect on the bioresponse. Appropriately scaled engineered microtopographies replicated in the silicone elastomer can produce a 250% increase in algal zoospore fouling or an 85% reduction in settlement relative to a smooth silicone elastomer. Finally, the modification of the surface energy of this material was achieved by acid catalyzed surface hydrolysis and subsequent grafting of poly(ethylene glycol), polysulfone, or perfluoropolyether. The water contact angle could be increased by 16% or decreased by 60% relative to the silicone elastomer control. These surfaces were characterized by various contact angle techniques, ATR-FTIR, and XPS. These surface grafts were also combined with the topographical modifications to evaluate the relative significance of these two factors on bioresponse.

  1. Water diffusion within hydrated model grafted polymeric membranes with bimodal side chain length distributions.

    PubMed

    Dorenbos, G

    2015-04-14

    The effect of bimodal side chain length distributions on pore morphology and solvent diffusion within hydrated amphiphilic polymeric membranes is predicted. Seven polymeric architectures are constructed from hydrophobic backbones from which at regular intervals side chains branch off that are alternatingly short (composed of p hydrophobic A fragments or beads) and long (q A fragments, q > p). The side chains are end-linked with a hydrophilic C fragment. Pore morphologies at a water volume fraction of 0.16 are calculated by dissipative particle dynamics (DPD). Water diffusion through the water containing pores is calculated by tracer diffusion calculations through 140 selected snapshots and from the water bead motions. Diffusion constants decrease with difference in side chain lengths, q - p. Overall, the distance between pores also decreases with q - p. The results are explained by counting for every architecture the average number of bonds 〈N(bond)〉 between an A and the nearest C fragment. These results are in line with a database that contains more than 60 architectures. Diffusion constants tend to increase linearly with 〈N(bond)〉|C|(-1)|A|, where |C| and |A| are the C and A bead fractions within the architecture. 〈N(bond)〉 is therefore expected to be an interesting design parameter for obtaining low percolation thresholds for solvent and/or proton diffusion. PMID:25703230

  2. New Applications of Ring-Opening Metathesis Polymerization for Grafting Alkylene Oxide-Based Copolymers

    NASA Astrophysics Data System (ADS)

    Spurcaciu, Bogdan; Buzdugan, Emil; Nicolae, Cristian; Ghioca, Paul; Iancu, Lorena; Dragutan, Valerian; Dragutan, Ileana

    This research tackles the challenges of innovative modification of poly(allyl alkylene oxides) by ROMP to produce new materials. Firstly, binary and ternary copolymers, poly(epichlorohydrin-allyl glycidyl ether) (ECH-AGE) and poly (epichlorohydrin-propylene oxide-allyl glycidyl ether) (ECH-PO-AGE), have been prepared using as initiator a catalytic system consisting of an alkyl aluminium, controlled amounts of water and different compounds (ethers, diols, phosphines, salicylic acid derivatives, organozincs) acting as cocatalysts. Among catalysts explored in these copolymerizations most productive showed to be the systems triisobutylaluminium (TIBA), water and Zn(DIPS)2 or Zn(acac)2. Copolymers which have become thus available were subsequently grafted onto the pendent allylic groups by ROMP with cycloolefins (cyclooctene, norbornene, cyclododecene) involving ruthenium based catalysts.

  3. Preparation of Mg(OH)2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

    2016-02-01

    Mg(OH)2 flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH)2 hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH)2 pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH)2 crystals and affect the formation of lamella-like Mg(OH)2 crystals. The cellulose fiber grafted with modified Mg(OH)2 hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

  4. Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis Cells: Evaluation of Key Membrane Properties.

    PubMed

    Albert, Albert; Barnett, Alejandro O; Thomassen, Magnus S; Schmidt, Thomas J; Gubler, Lorenz

    2015-10-14

    Radiation-grafted membranes can be considered an alternative to perfluorosulfonic acid (PFSA) membranes, such as Nafion, in a solid polymer electrolyte electrolyzer. Styrene, acrylonitrile, and 1,3-diisopropenylbenzene monomers are cografted into preirradiated 50 μm ethylene tetrafluoroethylene (ETFE) base film, followed by sulfonation to introduce proton exchange sites to the obtained grafted films. The incorporation of grafts throughout the thickness is demonstrated by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis of the membrane cross-sections. The membranes are analyzed in terms of grafting kinetics, ion-exchange capacity (IEC), and water uptake. The key properties of radiation-grafted membranes and Nafion, such as gas crossover, area resistance, and mechanical properties, are evaluated and compared. The plot of hydrogen crossover versus area resistance of the membranes results in a property map that indicates the target areas for membrane development for electrolyzer applications. Tensile tests are performed to assess the mechanical properties of the membranes. Finally, these three properties are combined to establish a figure of merit, which indicates that radiation-grafted membranes obtained in the present study are promising candidates with properties superior to those of Nafion membranes. A water electrolysis cell test is performed as proof of principle, including a comparison to a commercial membrane electrode assembly (MEA). PMID:26393461

  5. Modification on liquid retention property of cassava starch by radiation grafting with acrylonitrile. I. Effect of γ-irradiation on grafting parameters

    NASA Astrophysics Data System (ADS)

    Kiatkamjornwong, S.; Chvajarernpun, J.; Nakason, C.

    1993-07-01

    Radiation modification on liquid retention properties of native cassava starch, gelatinized at 85°C, by graft copolymerization with acrylonitrile was carried out by mutual irradiation to gamma-rays. A thin aluminum foil was used to cover the inner wall of the reaction vessel, so that the homopolymer concentration was reduced to be less than 1.0% with a distilled water retention value of 665 g/g of the dry weight of the saponified grafted product. Confirmation of graft copolymerization and saponification reactions was made by the infrared spectrophotometric technique. The combined effect of radiation parameters in terms of an irradiation time and a dose rate to the total dose on the extent of the grafting reaction expressed in terms of grafting parameters which directly influenced liquid retention values was evaluated in conjunction with statistical analysis.

  6. Characterization of Bonding Between Poly(dimethylsiloxane) and Cyclic Olefin Coplymer Using Corona Discharge Induced Grafting Polymerization

    PubMed Central

    Liu, Ke; Gu, Pan; Hamaker, Kiri; Fan, Z. Hugh

    2011-01-01

    Thermoplastics have been increasingly used for fabricating microfluidic devices because of their low cost, mechanical/biocompatible attributes, and well-established manufacturing processes. However, there is sometimes a need to integrate such a device with components made from other materials such as polydimethylsiloxane (PDMS). Bonding thermoplastics with PDMS to produce hybrid devices is not straightforward. We have reported our method to modify the surface property of a cyclic olefin copolymer (COC) substrate by using corona discharge and grafting polymerization of 3-(trimethoxysilyl)propyl methacrylate; the modified surface enabled strong bonding of COC with PDMS. In this paper, we report our studies on the surface modification mechanism using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurement. Using this bonding method, we fabricated a three-layer (COC/PDMS/COC) hybrid device consisting of elastomer-based valve arrays. The microvalve operation was confirmed through the displacement of a dye solution in a fluidic channel when the elastomer membrane was pneumatically actuated. Valve-enabled microfluidic handling was demonstrated. PMID:21962541

  7. Benzophenone absorption and diffusion in poly(dimethylsiloxane) and its role in graft photo-polymerization for surface modification.

    PubMed

    Schneider, Marc H; Tran, Yvette; Tabeling, Patrick

    2011-02-01

    Following the great success of traditional microfluidic devices across many disciplines, a new class of microfluidic systems emerged in recent years, which features finely tuned, localized surface modifications within the microstructures in order to keep up with the demand for devices of ever increasing complexity (lab on chip, assay on chip, etc.). Graft photopolymerization has become a powerful tool for such localized surface modifications particularly in combination with poly(dimethylsiloxane) (PDMS) devices, as it is compatible with many functional monomers and allows for high spatial resolution. However, application within enclosed PDMS microstructures and in particular well-controlled surface-directed polymerization remains challenging. Detailed understanding of the interaction between photoinitiator, benzophenone (BP), and polymer matrix is needed. We have developed a visualization technique, which allows for observation of reacted BP in situ within the PDMS matrix. We present a detailed study on solvent-driven BP diffusion providing results essential to successful surface treatment. We also identified and investigated photoinitiator inhibition by oxygen and provide appropriate mitigation strategies. PMID:21207954

  8. Functional polymer brushes via surface-initiated atom transfer radical graft polymerization for combating marine biofouling.

    PubMed

    Yang, Wen Jing; Neoh, Koon-Gee; Kang, En-Tang; Lee, Serina Siew Chen; Teo, Serena Lay-Ming; Rittschof, Daniel

    2012-01-01

    Dense and uniform polymer brush coatings were developed to combat marine biofouling. Nonionic hydrophilic, nonionic hydrophobic, cationic, anionic and zwitterionic polymer brush coatings were synthesized via surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-hydroxyethyl methacrylate, 2,3,4,5,6-pentafluorostyrene, 2-(methacryloyloxy)ethyl trimethylammonium chloride, 4-styrenesulfonic acid sodium and N,N'-dimethyl-(methylmethacryloyl ethyl) ammonium propanesulfonate, respectively. The functionalized surfaces had different efficacies in preventing adsorption of bovine serum albumin (BSA), adhesion of the Gram-negative bacterium Pseudomonas sp. NCIMB 2021 and the Gram-positive Staphylococcus aureus, and settlement of cyprids of the barnacle Amphibalanus amphitrite (=Balanus amphitrite). The nonionic hydrophilic, anionic and zwitterionic polymer brushes resisted BSA adsorption during a 2 h exposure period. The nonionic hydrophilic, cationic and zwitterionic brushes exhibited resistance to bacterial fouling (24 h exposure) and cyprid settlement (24 and 48 h incubation). The hydrophobic brushes moderately reduced protein adsorption, and bacteria and cyprid settlement. The anionic brushes were least effective in preventing attachment of bacteria and barnacle cyprids. Thus, the best approach to combat biofouling involves a combination of nonionic hydrophilic and zwitterionic polymer brush coatings on material surfaces. PMID:22963034

  9. Modification of nylon-6 fibres by radiation-induced graft polymerisation of vinylbenzyl chloride

    NASA Astrophysics Data System (ADS)

    Ting, T. M.; Nasef, Mohamed Mahmoud; Hashim, Kamaruddin

    2015-04-01

    Modification of nylon-6 fibres by radiation-induced graft copolymerisation (RIGP) of vinylbenzyl chloride (VBC) using the preirradiation method was investigated. A number of grafting parameters such as type of solvent, total dose, monomer concentrations, reaction temperature and reaction time were studied to obtain desired degree of grafting (DG). The DG was found to be a function of reaction parameters and achieved a maximum value of 130 wt% at 20 vol% VBC concentration in methanol, 300 kGy dose, 30 °C temperature and 3 h reaction time. Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to evaluate the chemical, morphological and structural changes that occurred in the grafted fibres, respectively. Thermogravimetric analysis (TGA) was also applied to determine the thermal stability, whereas differential scanning calorimeter (DSC) and universal mechanical tester were used to analyse respective thermal and mechanical properties of the grafted fibres. The results of these analyses provide strong evidence for successful grafting of VBC onto nylon-6, and the variation in the properties of the grafted fibres depends on DG.

  10. Effect of acid on radiation grafting of functional monomers onto silicone rubber

    NASA Astrophysics Data System (ADS)

    Hongfei, Ha; Xiaohong, Lu; Jilan, Wu

    The acid effect in mutual radiation grafting of acrylic acid (AA), 4-vinyl-pyridine (4-VP) and N-2-vinylpyrrolidone (N-NP) in methanol on silicone rubber was investigated. Measurements of grafting yields as a function of dose were carried out. In addition, the effects of Cu 2+ and monomer concentrations in solvent were observed. It was found that acid in grafting system of 4-VP had enhancement effect, in N-VP system had inhibition effect with a wide absorbed dose range. But in the case of AA the relationship was more complex: below 6 kGy acid enhanced the grafting yield; while dose was up to 13 kGy the opposite results were obtained. The mechanisms of acid effects in the methanol systems were discussed.

  11. Radiation-grafting of thermo- and pH-responsive poly(N-vinylcaprolactam-co-acrylic acid) onto silicone rubber and polypropylene films for biomedical purposes

    NASA Astrophysics Data System (ADS)

    Ferraz, Caroline C.; Varca, Gustavo H. C.; Ruiz, Juan-Carlos; Lopes, Patricia S.; Mathor, Monica B.; Lugão, Ademar B.; Bucio, Emilio

    2014-04-01

    This work focuses on the effects of gamma-ray irradiation conditions on the stimuli-responsiveness of polypropylene (PP) films and silicone (SR) rubber substrates grafted with N-vinylcaprolactam (NVCL) and acrylic acid (AAc). PP films and SR rubber were modified by simultaneous polymerization and grafting of NVCL and AAc, using pre-irradiation oxidative method at a dose rate of 12.23 kGy h-1 and doses ranging from 5 to 70 kGy. NVCL and AAc solutions (1/1, v/v) at 50% monomer concentration (v/v) in toluene were added to the sample substrates, degassed, sealed and heated at 60 and 70 °C for 12 h. After grafting, the samples were soaked in ethanol and distilled water for 24 h successively, followed by drying under vacuum. Samples were characterized by FTIR-ATR, DSC and swelling measurements. Critical points (pH critical or LCST) of grafts were obtained in a pH-environment (pH ranges from 2.2 to 9) and in a thermo-environment (temperature ranges from 22 to 50 °C). Cytotoxicity evaluation was performed using fibroblast BALB/c 3T3 cells. The relationship between NVCL-co-AAc grafting and radiation dose was different for each substrate, PP and SR. At 50% NVCL/AAc concentration in toluene, grafting values were higher for SR than for PP. Despite the fact that PP-g-(NVCL-co-AAc) membrane presented a cytotoxic profile at the highest experimental concentration assayed, cytotoxicity evaluation revealed noncytotoxic profiles for the membranes synthesized highlighting their applications for biomedical purposes.

  12. Radiation induced grafting of some vinyl monomers on cotton fabric for improved properties. I—Grafting with styrene

    NASA Astrophysics Data System (ADS)

    Zahran, A. H.; Dessouki, A. M.; Abo Zeid, M.

    Cotton fabric has been grafted by styrene using the direct irradiation method. Mixture of toluene and methanol was used to dilute styrene in the grafting solution. The effect of irradiation dose, solvent, and monomer concentration were investigated. Crease recovery was measured as a function of the grafting percentage. It was found that the crease recovery shows a good improvement even at low grafting percentage. Grafted samples gained the ability to be dyed with disperse dyes. Grafted samples containing as low as 2.5% polystyrene show good affinity towards disperse dyes. Moreover, it shows a homogeneous distribution of the grafted chains through the fabric. The tensile properties of the grafted fabric was also measured as a function of the grafting percentage.

  13. Subacute radiation dermatitis: a histologic imitator of acute cutaneous graft-versus-host disease

    SciTech Connect

    LeBoit, P.E.

    1989-02-01

    The histopathologic changes of radiation dermatitis have been classified either as early effects (necrotic keratinocytes, fibrin thrombi, and hemorrhage) or as late effects (vacuolar changes at the dermal-epidermal junction, atypical radiation fibroblasts, and fibrosis). Two patients, one exposed to radiation therapeutically and one accidentally, are described. Skin biopsy specimens showed an interface dermatitis characterized by numerous dyskeratotic epidermal cells with lymphocytes in close apposition (satellite cell necrosis); that is, the epidermal changes were similar to those in acute graft-versus-host disease. Because recipients of bone marrow transplants frequently receive total body irradiation as part of their preparatory regimen, the ability of radiation to cause persistent epidermal changes similar to those in acute graft-versus-host disease could complicate the interpretation of posttransplant skin biopsy specimens.

  14. Biocompatibility of polypropylene non-woven fabric membrane via UV-induced graft polymerization of 2-acrylamido-2-methylpropane sulfonic acid

    NASA Astrophysics Data System (ADS)

    Song, Lingjie; Zhao, Jie; Yang, Huawei; Jin, Jing; Li, Xiaomeng; Stagnaro, Paola; Yin, Jinghua

    2011-10-01

    This work described the graft polymerization of a sulfonic acid terminated monomer, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), onto the surface of polypropylene non-woven (NWF PP) membrane by O 2 plasma pretreatment and UV-induced photografting method. The chemical structure and composition of the modified surfaces were analyzed by FTIR-ATR and XPS, respectively. The wettability was investigated by water contact angle and equilibrium water adsorption. And the biocompatibility of the modified NWF PP membranes was evaluated by protein adsorption and platelet adhesion. It was found that the graft density increased with prolonging UV irradiation time and increasing AMPS concentration; the water contact angles of the membranes decreased from 124° to 26° with the increasing grafting density of poly(AMPS) from 0 to 884.2 μg cm -2, while the equilibrium water adsorption raised from 5 wt% to 75 wt%; the protein absorption was effectively suppressed with the introduction of poly(AMPS) even at the low grafting density (132.4 μg cm -2); the number of platelets adhering to the modified membrane was dramatically reduced when compared with that on its virgin surface. These results indicated that surface modification of NWF PP membrane with AMPS was a facile approach to construct biocompatible surface.

  15. Specialty polymeric membranes. 8: Separation of benzene from benzene/cyclohexane mixtures with nylon 6-graft-poly(butyl methacrylate) membranes

    SciTech Connect

    Yoshikawa, Masakazu; Tsubouchi, Keisuke; Kitao, Toshio

    1999-02-01

    A novel pervaporation membrane was prepared by radical graft polymerization of butyl methacrylate onto nylon 6. The permselectivity toward benzene was increased by the introduction of poly(butyl methacrylate) onto a nylon 6 membrane. From pervaporation and sorption experiments, it was shown that the introduction of poly(butyl methacrylate) onto a nylon 6 membrane leads to the enhancement of permselectivity toward benzene. The solubility data for benzene were described by a combination of simple sorption and specific sorption, while cyclohexane solubility was described by simple sorption.

  16. [Evaluation of Radiation Dose during Stent-graft Treatment Using a Hybrid Operating Room System].

    PubMed

    Haga, Yoshihiro; Chida, Kouichi; Kaga, Yuji; Saitou, Kazuhisa; Arai, Takeshi; Suzuki, Shinichi; Iwaya, Yoshimi; Kumasaka, Eriko; Kataoka, Nozomi; Satou, Naoto; Abe, Mitsuya

    2015-12-01

    In recent years, aortic aneurysm treatment with stent graft grafting in the X-ray fluoroscopy is increasing. This is an endovascular therapy, because it is a treatment which includes the risk of radiation damage, having to deal with radiation damage, to know in advance is important. In this study, in order to grasp the trend of exposure stent graft implantation in a hybrid operating room (OR) system, focusing on clinical data (entrance skin dose and fluoroscopy time), was to count the total. In TEVAR and EVAR, fluoroscopy time became 13.40 ± 7.27 minutes, 23.67 ± 11.76 minutes, ESD became 0.87 ± 0.41 mGy, 1.11 ± 0.57 mGy. (fluoroscopy time of EVAR was 2.0 times than TEVAR. DAP of EVAR was 1.2 times than TEVAR.) When using the device, adapted lesions and usage are different. This means that care changes in exposure-related factors. In this study, exposure trends of the stent graft implantation was able to grasp. It can be a helpful way to reduce/optimize the radiation dose in a hybrid OR system. PMID:26685833

  17. In-situ formation of silver nanoparticles on poly (lactic acid) film by γ-radiation induced grafting of N-vinyl pyrrolidone.

    PubMed

    Wang, Jingxia; Chen, Hao; Chen, Zhuping; Chen, Yuheng; Guo, Dan; Ni, Maojun; Liu, Siyang; Peng, Chaorong

    2016-06-01

    A fast, easy and novel method for preparing biodegradable polymer films with silver nanoparticles was investigated to endow the material with excellent biocompatibility and antibacterial property. Silver nanoparticles (Ag NPs) were immobilized on the surface of polylactic acid (PLA) film by gamma radiation induced grafting of N-vinyl pyrrolidone (NVP). In this method, poly (N-vinyl pyrrolidone) (PVP) was produced and grafted onto the surface of PLA film by gamma radiation polymerization of NVP. PVP acted as both a bridge to connect the Ag NPs with the PLA film, and a stabilizer to protect the Ag NPs from agglomeration. The effect of various reaction parameters, including NVP/Ag mole ratio and radiation dose, on the fabrication of PLA-g-NVP/Ag film was demonstrated. Moreover, the interaction between PVP and Ag NPs was studied by X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, that revealed the Ag NPs coordinated through the oxygen atom on the carbonyl group of PVP at 15kGy radiation dose, but through the nitrogen atom and the oxygen atom of the amide group of PVP at 1kGy dose. PMID:27040205

  18. Modification of fiber properties through grafting of acrylonitrile to rayon by chemical and radiation methods.

    PubMed

    Kaur, Inderjeet; Sharma, Neelam; Kumari, Vandna

    2013-11-01

    Fibrous properties of rayon has been modified through synthesis of graft copolymers of rayon with acrylonitrile (AN) by chemical method using ceric ammonium nitrate (CAN/HNO3) as a redox initiator and gamma radiation mutual method. Percentage of grafting (Pg) was determined as a function of initiator concentration, monomer concentration, irradiation dose, temperature, time of reaction and the amount of water. Maximum percentage of grafting (160.01%) using CAN/HNO3 was obtained at [CAN] = 22.80 × 10(-3) mol/L, [HNO3] = 112.68 × 10(-2) mol/L and [AN] = 114.49 × 10(-2) mol/L in 20 mL of water at 45 °C within 120 min while in case of gamma radiation method, maximum Pg (90.24%) was obtained at an optimum concentration of AN of 76.32 × 10(-2) mol/L using 10 mL of water at room temperature with total dose exposure of 3.456 kGy/h. The grafted fiber was characterized by FTIR, SEM, TGA and XRD studies. Swelling behavior of grafted rayon in different solvents such as water, methanol, ethanol, DMF and acetone was studied and compared with the unmodified rayon. Dyeing behavior of the grafted fiber was also investigated. PMID:25685464

  19. Laser radiation in the treatment of prosthetic graft stenosis. A preliminary study of prosthesis damage by laser energy

    SciTech Connect

    Seeger, J.M.; Abela, G.S.; Klingman, N.

    1987-09-01

    Transluminal laser recanalization is potentially an important new treatment of anastomotic intimal hyperplasia. However, currently used grafts or sutures may be damaged by laser radiation at power and energy levels required for plaque removal. To investigate this problem, two commonly used grafts (Dacron and polytetrafluoroethylene (PTFE)) and two types of vascular suture (polypropylene and PTFE) were exposed to argon laser radiation in vitro. Dacron and PTFE grafts recovered from amputations were also studied to determine whether graft healing affected graft resistance to laser damage. Power and energy levels required to perforate atherosclerotic superficial femoral arteries were determined for comparison. PTFE grafts were significantly (1.5 to 7 times) more resistant to perforation by laser energy than atherosclerotic arteries under all conditions. In contrast, Dacron grafts perforated at power and energy levels one half to one third of that required for vaporization of atherosclerotic plaque. PTFE sutures remained intact at power and energy levels above the levels that perforated atherosclerotic arteries, whereas polypropylene sutures were destroyed by very low levels of power and energy (0.5 joules at 0.5 watts). Because of the variable levels of power and energy that damage different types of prosthetic grafts and sutures, laser angioplasty should only be investigated clinically as a therapy for anastomotic intimal hyperplasia when PTFE grafts and sutures are present.

  20. Influence of Space Radiation on the Outgassing Rate of a Patterned Polymeric Composite in Vacuum

    SciTech Connect

    Khasanshin, R. H.; Timofeev, A. N.; Ivanov, M. F.

    2009-01-05

    Experimental results on outgassing rates of patterned polymeric composites preliminary subjected to separate and combined radiation have been analyzed and presented. Mathematical models describing the outgassing processes in these materials were used for interpretation of the experimental data. Numerical results found using the models are presented.

  1. Swelling characteristics of konjac glucomannan superabsobent synthesized by radiation-induced graft copolymerization

    NASA Astrophysics Data System (ADS)

    Wu, Jia; Deng, Xiao; Lin, Xiangyang

    2013-02-01

    Graft copolymerization of konjac glucomannan (KGM) and acrylic acid was induced by 60Co-γ irradiation at room temperature. The effects of radiation dose and monomer-to-KGM ratio on grafting yield and equilibrium water absorbency were investigated. The KGM-based superabsorbent polymer (KSAP) could absorb water 625 times of its dry weight when the radiation dose was 5.0 kGy and monomer-to-KGM ratio was 5. The structure of KSAP was characterized by FTIR, XRD, and SEM. KSAP showed a lower crystallinity than KGM. The porous microstructure of KSAP was revealed by SEM. The diffusion mechanism of water in the hydrogel is consistent with the anomalous diffusion model. Cations, especially multivalent cations, greatly reduced water absorbency of KSAP. Rising temperature, acidic or basic solutions are not favorable for the swelling of KSAP.

  2. Radiation-induced grafting of vinylbenzyltrimethylammonium chloride (VBT) onto cotton fabric and study of its anti-bacterial activities

    NASA Astrophysics Data System (ADS)

    Kumar, Virendra; Bhardwaj, Y. K.; Rawat, K. P.; Sabharwal, S.

    2005-06-01

    Mutual radiation grafting technique using 60Co gamma radiation has been used to carry out grafting of vinylbenzyltrimethylammonium chloride (VBT) onto cotton cellulose substrate. Grafting yield increased with radiation dose and decreased with dose rate but was adversely affected by the presence of O 2 and salts of Fe 2+ and Cu 2+. However, the presence of an acid did not affect grafting in the concentration range studied. The effect of organic solvents like methanol, ethanol, n-propanol, iso-propanol, tert-butanol on grafting yield was investigated in the mixed aqueous solvent system. The VBT grafted cotton samples showed significantly higher water uptake and water retention properties and possessed excellent anti-bacterial activity against strains like Escherichia coli and Staphylococcus aureus. Samples with 25% grafting extent showed 6 log cycles reduction in bacterial counts within 6 h of exposure time. The anti-bacterial activity of the grafted cotton samples was retained after several cycles of washing and drying in a commercial detergent powder.

  3. Modification of flax fibres by radiation induced emulsion graft copolymerization of glycidyl methacrylate

    NASA Astrophysics Data System (ADS)

    Moawia, Rihab Musaad; Nasef, Mohamed Mahmoud; Mohamed, Nor Hasimah; Ripin, Adnan

    2016-05-01

    Flax fibres were modified by radiation induced graft copolymerization of glycidyl methacrylate (GMA) by pre-irradiation method in an emulsion medium. The effect of reaction parameters on the degree of grafting (DOG) such as concentration of bleaching agent, absorbed dose, monomer concentration, temperature and reaction time were investigated. The DOG was found to be dependent on the investigated parameters. The incorporation of poly(GMA) grafts in the bleached flax fibres was confirmed by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The structural and mechanical changes were evaluated by X-ray diffraction (XRD) and mechanical tester, respectively. The results revealed that reacting bleached flax fibres irradiated with 20 kGy with 5% GMA emulsion containing 0.5% polyoxyethylene-sorbitan monolaurate (Tween 20) surfactant at 40 °C for 1 h led to a maximum DOG of 148%. The grafted fibres showed sufficient mechanical strength and hydrophobicity which make them promising precursors for development of adsorbents after appropriate chemical treatments.

  4. Time resolved study of the high energy radiation initiated polymerization

    NASA Astrophysics Data System (ADS)

    Takács, E.; Wojnárovits, L.

    1995-11-01

    The EB (electron beam) initiated polymerization of ethyl acrylate (EA) and ethyl methacrylate (EMA) in dilute cyclohexane solution was studied by pulse radiolysis technique with transient spectroscopic detection. The maximum in the absorption spectrum of the intermediates lies at λ = 290-320 nm in EA solution and at λ = 285 in EMA solution. The extinction coefficients of the intermediates at the maximum of the spectrum were calculated to be ɛ285nm ˜ 700 mol -1 dm 3 cm -1 in EMA solution and ɛ290-320nm ˜ 300 mol -1 dm 3 cm -1 in EA solution. From the decay curves rate parameters of termination (2 kt) were calculated. The decays were generally found to be second order with a rate coefficient of 1.4 × 10 9mol -1 dm 3 s -1 in EMA solutions and 6 × 10 8mol -1 dm 3 s -1 in EA solutions. In some cases deviation from a single second order was observed. This was interpreted in terms of the hindered mobility of the growing radicals.

  5. Influence of matrix porosity on the immobilization of penicillin acylase by radiation-induced polymerization

    NASA Astrophysics Data System (ADS)

    Carenza, M.; Lora, S.; Palma, G.; Boccù, E.; Largajolli, R.; Veronese, F. M.

    Penicillin acylase was immobilized by low temperature radiation-induced polymerization into polymer matrices obtained from monomers of different hydrophilicities, at various ratios of monomer to enzyme solution and at different polymerization conversions. It was found that the penicillin acylase retention (60-85% of the starting enzyme) is independent of the monomer used in thepolymerization, of the polymerization conversion and of the porosity of the polymer matrix. On the other hand, the penicillin acylase retention strongly depends on the presence in the irradiation mixture of the hydrophobic crosslinking agent, trimethylolpropane trimethacrylate, even in low amounts. The data suggest that the enzyme is bound to the polymer matrix by hydrophobic interactions through crosslinking agent molecules.

  6. Radiation grafted and sulfonated (FEP-g-polysterene) - An alternative to perfluorinated membranes for PEM fuel cells?

    NASA Astrophysics Data System (ADS)

    Buechi, F. N.; Gupta, B.; Rouilly, M.; Hauser, P. C.; Chapiro, A.; Scherer, G. G.

    Partially fluorinated proton exchange membranes (PEMs) were synthesized for fuel cell applications by simultaneous radiation grafting of styrene on FEP films followed by sulfonation. Properties of the synthesized membranes can be tailored by varying the degree of grafting and crosslinking. The performance of these membranes was tested in H2/O2 fuel cells. Long time testing showed steady performance for high grafted membranes over periods of more than 300 h at a cell temperature of 60 C. Low grafted membranes and the Morgane CDS membrane showed considerable decay of cell power on the same time scale. A fast degradation of all membranes occurred at a cell temperature of 80 C. It is noted that grafting in film form makes this process a potentially cheap and easy technique for the preparation of solid polymer fuel cell electrolytes.

  7. Radiation induced graft copolymerization of n-butyl acrylate onto poly(ethylene terephthalate) (PET) films and thermal properties of the obtained graft copolymer

    NASA Astrophysics Data System (ADS)

    Ping, Xiang; Wang, Mozhen; Ge, Xuewu

    2011-05-01

    n-Butyl acrylate (BA) was successfully grafted onto poly(ethylene terephthalate) (PET) film using simultaneous radiation induced graft copolymerization with gamma rays. When BA concentration ranges from 20% to 30%, the Degree of Grafting (DG), measured by gravimetry and 1H NMR, increases with the monomer concentration and absorbed dose, but decreases with dose rate from 0.83 to 2.53 kGy/h. The maximum DG can reach up to 22.1%. The thermal transition temperatures such as glass-transition temperature ( Tg) and cold-crystallization temperature ( Tcc) of PET in grafted films were little different from those in original PET film, indicating that microphase separation occurred between PBA side chains and PET backbone. This work implied that if PET/elastomers (e.g., acrylate rubber) blends are radiated by high energy gamma rays under a certain condition, PET-g-polyacrylate copolymer may be produced in-situ, which will improve the compatibility between PET and the elastomers so as to improve the integral mechanical properties of PET based engineering plastic.

  8. Poly(2-hydroxyethyl methacrylate) grafted halloysite nanotubes as a molecular host matrix for luminescent ions prepared by surface-initiated RAFT polymerization and coordination chemistry

    NASA Astrophysics Data System (ADS)

    Islam, Md. Rafiqul; Bach, Long Giang; Lim, Kwon Taek

    2013-07-01

    A fluorescent nanohybrid complex comprising of halloysite nanotubes (HNTs), poly(2-hydroxyethyl methacrylate) (PHEMA), and europium ions (Eu3+) was synthesized by the combination of surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization and coordination chemistry. Initially, PHEMA was grafted from the HNTs by SI-RAFT and then reacted with succinic anhydride to provide carboxyl acid groups on the external layers of HNTs-g-PHEMA nanohybrids. The subsequent coordination of the nanohybrids with Eu3+ ions afforded photoluminescent Eu3+ tagged HNTs-g-PHEMA nanohybrid complexes (HNTs-g-PHEMA-Eu3+). The structure, morphology, and fluorescence properties of the Eu3+ coordinated nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR, XPS, and EDS analyses suggested the formation of the HNTs-g-PHEMA-Eu3+ nanohybrids. FE-SEM images indicated the immobilization of polymer layers on HNTs. TGA scans further demonstrated the grafting of PHEMA onto HNTs surface. The optical properties of HNTs-g-PHEMA-Eu3+ nanohybrid complexes were investigated by photoluminescence spectroscopy.

  9. Revival of the R-group approach: a "CTA-shuttled" grafting from approach for well-defined cylindrical polymer brushes via RAFT polymerization.

    PubMed

    Zheng, Zhicheng; Ling, Jun; Müller, Axel H E

    2014-01-01

    The synthesis of well-defined cylindrical polymer brushes (CPBs) from a linear polymer backbone with a high density of RAFT functionalities ("grafting from" approach) is challenging when the chain transfer agent (CTA) is attached to the backbone via its R-group. It is proposed that the difficulties of the R-group approach in controlling the grafting polymerization are induced by the "entrapment" of active free radicals within individual growing CPBs. A facile "CTA-shuttled" R-group approach overcoming this entrapment effect is developed, and used to synthesize well-defined CPBs with polystyrene or poly(tert-butyl acrylate) branches and core-shell CPBs with polystyrene-block-poly(N-isopropylacrylamide) branches. The polydispersity index (PDI = 1.23) of the obtained CPBs with polystyrene branches is much lower than that from the conventional R-group approach (PDI = 2.18). Monte Carlo simulations confirm that the advantage of the "CTA-shuttled" R-group approach consists in the release of the active radicals from the trapping CPB systems. PMID:24115272

  10. Shelf life prediction of radiation sterilized polymeric materials

    NASA Astrophysics Data System (ADS)

    Sandford, Craig; Woo, Lecon

    The functional properties of many polymers employed in medical disposables are unaffected by sterilizing doses of ionizing radiation. However, some materials (PVC, polypropylene, cellulosics, etc.) undergo undesirable changes which continue to occur for the shelf life of the product. In many cases, conventional accelerated aging techniques do not accurately predict the real time properties of the materials. As real time aging is not generally practical, it has become necessary to develop accelerated aging techniques which can predict the functional properties of a material for the shelf life of the product. This presentation will address issues involved in developing these tests. Real time physical property data is compared to data generated by various acceleration methods.

  11. Fundamental investigation of ultraviolet radiation effects in polymeric film-forming materials

    NASA Technical Reports Server (NTRS)

    Giori, C.; Yamauchi, T.; Llewellen, P.; Gilligan, J.

    1974-01-01

    A literature search from 1958 to present was conducted on the effect of ultraviolet radiation on polymeric materials, with particular emphasis on vacuum photolysis, mechanisms of degradation, and energy transfer phenomena. The literature from 1958 to 1968 was searched manually, while the literature from 1968 to present was searched by using a computerized keyword system. The primary objective was to provide the necessary background information for the design of new or modified materials with improved stability to the vacuum-radiation environment of space.

  12. Cell culture on polymers prepared by radiation-induced polymerization of various glass-forming monomers.

    PubMed

    Yoshii, F; Kaetsu, I

    1983-04-01

    The growth of cells on polymers prepared by the radiation polymerization of monomethacrylate and dimethacrylate was investigated. Cell growth was affected greatly by such properties of the polymers as water content, wettability, and porosity. Growth was promoted remarkably by rinsing the polymers with warm water at 60-70 degrees C and by irradiation of polymers with an electron beam. Cell growth decreased with increasing oxyethylene length (n) in the polymerized dimethacrylate of same series, CH2C(CH3)CO(OCH2CH2)nOCOC(CH3)CH2. A decrease in the hydrophilicity of the polymer increased cell growth rate. Formation of pore structures in the polymer films also increased the cell growth. PMID:6679189

  13. Selective Fragmentation of Radiation-Sensitive Novel Polymeric Resist Materials by Inner-Shell Irradiation.

    PubMed

    Chagas, Gabriela Ramos; Satyanarayana, Vardhineedi Sri Venkata; Kessler, Felipe; Belmonte, Guilherme Kretzmann; Gonsalves, Kenneth E; Weibel, Daniel Eduardo

    2015-08-01

    Two key concepts in extreme ultraviolet lithography (EUVL) are important for it to be a candidate for the mass production of future integrated circuits: the polymer formulation and the photofragmentation process. In this work, both concepts were carefully studied. The design and synthesis of radiation-sensitive organic polymeric materials based on the inclusion of a radiation-sensitive tetrahydrothiophenium functional group are outlined. A 1-(4-methacryloyoxy)naphthalene-1-yl)tetrahydro-1H-thiophenium trifluoromethanesulfonate (MANTMS) monomer containing the tetrahydrothiophenium group undergoes homo- and copolymerizations using free-radical polymerization with a 2,2'-azobis(isobutyronitrile) initiator. The surface photodegradation and oxidation of these novel polymeric materials were investigated using highly monochromatized soft X-rays from synchrotron radiation at the carbon K-edge excitation region. An efficient functionalization was observed when the excitation energy was tuned to C 1s → π*C═C. A high rate of defluorination and a loss of sulfonated groups as a result of an increase in the irradiation time for the MANTMS homopolymer thin films were mainly observed under the π*C═C excitation of the naphthyl functional groups. On the contrary, excitation similar to C 1s → π*C═O or C 1s → σ*C-F did not produce important degradation, showing a highly selective process of bond breaking. Additionally, the presence of methyl methacrylate copolymer in the original MANTMS yielded a much higher degree of stability against inner-shell radiation damage. Our results highlight the importance of choosing the right polymer formulation and excitation energy to produce a sensitive material for EUVL without using the concept of chemical amplification. PMID:26158557

  14. PDMS-Glass bonding using grafted polymeric adhesive - Alternative process flow for compatibility with patterned biological molecules

    PubMed Central

    Beh, Cyrus Weijie; Zhou, Weizhuang

    2013-01-01

    We report a novel modification of silicone elastomer, polydimethylsiloxane (PDMS) with a polymer graft that allows interfacial bonding between elastomer and glass substrate to be performed without exposure of said substrate to harsh treatment conditions like oxygen plasma. Organic molecules can thus be patterned within microfluidic channels and still remain functional post-bonding. In addition, after polymer grafting the PDMS can be stored in a desiccator for at least 40 days, and activated upon exposure to acidic buffer for bonding. The bonded devices remain fully bonded in excess of 80 psi driving pressure, with no signs of compromise to the bond integrity. Finally, we demonstrate the compatibility of our method with biological molecules using a proof-of-concept DNA sensing device, in which fluorescently-labelled DNA targets are successfully captured by a patterned probe in a device sealed using our method, while the pattern on a plasma-treated device was completely destroyed. Therefore, this method provides a much-needed alternative bonding process for incorporation of biological molecules in microfluidic devices. PMID:22858861

  15. Radiation Protection Effectiveness of Polymeric Based Shielding Materials at Low Earth Orbit

    NASA Technical Reports Server (NTRS)

    Badavi, Francis F.; Stewart-Sloan, Charlotte R.; Wilson, John W.; Adams, Daniel O.

    2008-01-01

    Correlations of limited ionizing radiation measurements onboard the Space Transportation System (STS; shuttle) and the International Space Station (ISS) with numerical simulations of charged particle transport through spacecraft structure have indicated that usage of hydrogen rich polymeric materials improves the radiation shielding performance of space structures as compared to the traditionally used aluminum alloys. We discuss herein the radiation shielding correlations between measurements on board STS-81 (Atlantis, 1997) using four polyethylene (PE) spheres of varying radii, and STS-89 (Endeavour, 1998) using aluminum alloy spheres; with numerical simulations of charged particle transport using the Langley Research Center (LaRC)-developed High charge (Z) and Energy TRaNsport (HZETRN) algorithm. In the simulations, the Galactic Cosmic Ray (GCR) component of the ionizing radiation environment at Low Earth Orbit (LEO) covering ions in the 1< or equals Z< or equals 28 range is represented by O'Neill's (2004) model. To compute the transmission coefficient for GCR ions at LEO, O'Neill's model is coupled with the angular dependent LaRC cutoff model. The trapped protons/electrons component of LEO environment is represented by a LaRC-developed time dependent procedure which couples the AP8min/AP8max, Deep River Neutron Monitor (DRNM) and F10.7 solar radio frequency measurements. The albedo neutron environment resulting from interaction of GCR ions with upper atmosphere is modeled through extrapolation of the Atmospheric Ionizing Radiation (AIR) measurements. With the validity of numerical simulations through correlation with PE and aluminum spheres measurements established, we further present results from the expansion of the simulations through the selection of high hydrogen content commercially available polymeric constituents such as PE foam core and Spectra fiber(Registered TradeMark) composite face sheet to assess their radiation shield properties as compared to generic PE.

  16. Uranium sorption by Pseudomonas biomass immobilized in radiation polymerized polyacrylamide bio-beads.

    PubMed

    D'Souza, S F; Sar, Pinaki; Kazy, Sufia K; Kubal, B S

    2006-01-01

    A Pseudomonas strain identified as a potent biosorbent of uranium (U) and thorium was immobilized in radiation-induced polyacrylamide matrix for its application in radionuclide containing wastewater treatment. The immobilized biomass exhibited a high U sorption of 202 mg g(-1) dry wt. with its optimum at pH 5.0. A good fit of experimental data to the Freundlich model suggested multilayered uranium binding with an affinity distribution among biomass metal binding sites. Scanning electron microscopy revealed a highly porous nature of the radiation-polymerized beads with bacterial cells mostly entrapped on pore walls. Energy dispersive X-ray analysis (EDXA) coupled with SEM ascertained the accumulation of uranium by the immobilized biomass without any physical damage to the cells. A significant (90%) part of biosorbed uranium was recovered using sodium bicarbonate with the immobilized biomass maintaining their U resorption capacity for multiple sorption-desorption cycles. Uranium loading and elution behavior of immobilized biomass evaluated within a continuous up-flow packed bed columnar reactor showed its effectiveness in removing uranium from low concentration (50 mg U L(-1)) followed by its recovery resulting in a 4-5-fold waste volume reduction. The data suggested the suitability of radiation polymerization in obtaining bacterial beads for metal removal and also the potential of Pseudomonas biomass in treatment of radionuclide containing waste streams. PMID:16484078

  17. Immobilization of yeast cells on hydrogel carriers obtained by radiation-induced polymerization

    NASA Astrophysics Data System (ADS)

    Xin, Lu Zhao; Carenza, Mario; Kaetsu, Isao; Kumakura, Minoru; Yoshida, Masaru; Fujimura, Takashi

    Polymer hydrogels were obtained by radiation-induced copolymerization at -78°C of aqueous solutions of acrylic and methacrylic esters. The matrices were characterized by equilibrium water content measurements, by optical microscopy observations and by scanning electron microscopy analysis. Yeast cells were immobilized on these hydrogels and the ethanol productivity by batch fermentation was determined. Matrix hydrophilicity and porosity were found to deeply influence the adhesion of yeast cells and, hence, the ethanol productivity. The latter as well as other physico-chemical properties were also affected by the presence of a crosslinking agent added in small amounts to the polymerizing mixture.

  18. Radiation-induced grafting of styrene into poly(vinylidene fluoride) film by simultaneous method with two different solvents

    NASA Astrophysics Data System (ADS)

    Ferreira, H. P.; Parra, D. F.; Lugao, A. B.

    2012-09-01

    Radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses of 1 and 2.5 kGy in the presence of a styrene/N,N-dimethylformamide (DMF) solution (1:1, v/v) and at doses of 20, 40 and 80 kGy in presence of a styrene/toluene solution (1:1, v/v) at dose rate of 5 kGy h-1 was carried out by the simultaneous method under nitrogen atmosphere and room temperature, using gamma rays from a Co-60. The films were characterized before and after modification by calculated grafting yield (GY %), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). GY results shows that grafting increases with dose, and the grafting of styrene was confirm by FT-IR due to the new characteristic peaks and by the TG and DSC attributed to changes in thermal behavior of the grafted material. Results showed that the system allows the controlled grafting of styrene into PVDF using gamma rays at doses as low as 1 kGy in DMF.

  19. Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

    NASA Astrophysics Data System (ADS)

    Bach, Long Giang; Islam, Md. Rafiqul; Lee, Doh Chang; Lim, Kwon Taek

    2013-10-01

    A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

  20. Preparation of surface-imprinted polymer grafted with water-compatible external layer via RAFT precipitation polymerization for highly selective and sensitive electrochemical determination of brucine.

    PubMed

    Zhao, Lijuan; Zhao, Faqiong; Zeng, Baizhao

    2014-10-15

    A novel brucine imprinted polymer was prepared on multi-walled carbon nanotubes by reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization. The polymer was further grafted with hydrophilic poly(glycerol monomethacrylate) brushes to improve its water-compatibility. The obtained molecularly imprinted material showed enhanced accessibility to brucine and improved selective recognition property in water medium. When the material was supported on an ionic liquid functionalized graphene coated glassy carbon electrode for the electrochemical determination of brucine, the resulting electrochemical sensor presented good analytical performance. Under the optimized conditions, the peak current was linear to brucine concentration in the ranges of 0.006-0.6 μM and 0.6-5.0 μM with sensitivities of 15.3 μA/μMmm(2) and 5.4 μA/μM mm(2), respectively; the detection limit was 2 nM (S/N=3). The sensor was successfully applied to the determination of brucine in practical samples and the recovery for the standards added was 94-104%. PMID:24769450

  1. Radiation-induced graft copolymerization of poly(ethylene glycol) monomethacrylate onto deoxycholate-chitosan nanoparticles as a drug carrier

    NASA Astrophysics Data System (ADS)

    Pasanphan, Wanvimol; Rattanawongwiboon, Thitirat; Rimdusit, Pakjira; Piroonpan, Thananchai

    2014-01-01

    Poly(ethylene glycol) monomethacrylate-grafted-deoxycholate chitosan nanoparticles (PEGMA-g-DCCSNPs) were successfully prepared by radiation-induced graft copolymerization. The hydrophilic poly(ethylene glycol) monomethacrylate was grafted onto deoxycholate-chitosan in an aqueous system. The radiation-absorbed dose is an important parameter on degree of grafting, shell thickness and particle size of PEGMA-g-DCCSNPs. Owing to their amphiphilic architecture, PEGMA-g-DCCSNPs self-assembled into spherical core-shell nanoparticles in aqueous media. The particle size of PEGMA-g-DCCSNPs measured by TEM varied in the range of 70-130 nm depending on the degree of grafting as well as the irradiation dose. Berberine (BBR) as a model drug was encapsulated into the PEGMA-g-DCCSNPs. Drug release study revealed that the BBR drug was slowly released from PEGMA-g-DCCSNPs at a mostly constant rate of 10-20% in PBS buffer (pH 7.4) at 37 °C over a period of 23 days.

  2. Preparation of thermosensitive membranes by radiation grafting of acrylic acid/ N-isopropyl acrylamide binary mixture on PET fabric

    NASA Astrophysics Data System (ADS)

    Gupta, Bhuvanesh; Mishra, Swaiti; Saxena, Shalini

    2008-05-01

    Thermosensitive membranes were prepared by radiation-induced graft copolymerization of monomers on PET fabrics. A binary mixture of N-isopropyl acrylamide (NIPAAm) and acrylic acid (AA) was grafted on polyester fabric as a base material to introduce thermosensitive poly( N-isopropyl acrylamide) pendant chains having LCST slightly higher than 37 °C in the membrane. The influence of ferrous sulfate, radiation dose and monomer composition on the degree of grafting was studied. The structure of the grafted fabric was characterized by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The thermosensitive nature of the fabric was monitored by swelling at different temperatures. The graft copolymerization of AA with NIPAAm enhanced the LCST of the resultant membrane to ˜37 °C. The moisture vapor transmission rate (MVTR) and air permeability of the fabric decreased slightly, may be due to the slight blocking of the fabric pores. The immobilization of tetracycline hydrochloride as the model drug and its release characteristics at different temperatures were monitored.

  3. Peptide immobilization onto radiation grafted PVDF-g-poly(acrylic acid) films

    NASA Astrophysics Data System (ADS)

    Clochard, M.-C.; Betz, N.; Goncalves, M.; Bittencourt, C.; Pireaux, J.-J.; Gionnet, K.; Déléris, G.; Moël, A. Le

    2005-07-01

    Introducing hydrophilic functions on poly(vinylidene fluoride) (PVDF) films surface allows the covalent immobilization of peptides. Therefore radiation grafting of acrylic acid (AA) in pre-irradiated PVDF films was achieved to allow surface functionalization with linear and cyclic peptides. Peptides were bound via spacer molecules using EDC as a coupling agent. The reactions were followed by Fourier Transform Infrared (FTIR) spectroscopy in attenuated total reflection (ATR) mode. The amount of immobilized peptides was determined by UV spectroscopy. As well, an uncommon method for PVDF characterization and reactions quantification was used: high-resolution-magic angle spinning nuclear mass spectroscopy (HR-MAS NMR). Spacer saturation of the film surface corresponded to 25 mol% yield meaning that one spacer on 4 carboxylic acids was covalently bound. XPS experiments were also performed to deepen analysis of the surface composition. Peptide density is governed by steric hindrance. ELISA tests showed that the peptides' activity is maintained.

  4. Synthesis of poly(N-isopropylacrylamide) hydrogels by radiation polymerization and cross-linking

    SciTech Connect

    Nagaoka, Noriyasu; Kubota, Hitoshi; Katakai, Ryoichi; Safranj, Agneza; Yoshida, Masaru; Omichi, Hideki

    1993-12-20

    Poly(N-isopropylacrylamide) [poly(NIPAAm)] shows a typical thermal reversibility of phase transition in aqueous solutions. That is, it precipitates from solution above a critical temperature called the lower critical solution temperature (LCST) and dissolves below this temperature. When it is cross-linked, the obtained hydrogel collapses above LCST, while it swells and expands below LCST. This hydrogel has received much attention recently and has been used as a model system to demonstrate the validity of theories describing the coil-globule transition, swelling of networks, and folding and unfolding of biopolymers. It has also been proposed for various applications ranging from controlled drug delivery to solute separation. Poly(NIPAAm) hydrogel is usually synthesized at room temperature from an aqueous solution of the monomer by using a redox initiator composed of ammonium persulfate and N,N,N{prime},N{prime}-tetramethylethylenediamine in the presence of N,N{prime}-methylenebisacrylamide as a cross-linker. Since the LCST of poly(NIPAAm) is around 32 C, the polymerization at room temperature proceeds in a homogeneous solution. Recently, poly(NIPAAm) hydrogels were synthesized by starting the polymerization below the LCST and then elevating the temperature above it, by which method macroporous gels with fast temperature response were obtained. The idea is to apply a radiation--induced polymerization method for the synthesis of poly(NIPAAm) hydrogels. This method offers unique advantages for synthesis: it is a simple and additive-free process at all temperatures, and the degree of cross-linking can be easily controlled by irradiation conditions. Therefore, radiation methods are especially attractive for the synthesis of hydrogels with potential biomedical application where the residual chemical initiators may contaminate the product. It is possible to combine into one step the synthesis and sterilization of the product, and it is economically competitive.

  5. Gold-Loaded Polymeric Micelles for Computed Tomography-Guided Radiation Therapy Treatment and Radiosensitization

    PubMed Central

    2013-01-01

    Gold nanoparticles (AuNPs) have generated interest as both imaging and therapeutic agents. AuNPs are attractive for imaging applications since they are nontoxic and provide nearly three times greater X-ray attenuation per unit weight than iodine. As therapeutic agents, AuNPs can sensitize tumor cells to ionizing radiation. To create a nanoplatform that could simultaneously exhibit long circulation times, achieve appreciable tumor accumulation, generate computed tomography (CT) image contrast, and serve as a radiosensitizer, gold-loaded polymeric micelles (GPMs) were prepared. Specifically, 1.9 nm AuNPs were encapsulated within the hydrophobic core of micelles formed with the amphiphilic diblock copolymer poly(ethylene glycol)-b-poly(ε-capralactone). GPMs were produced with low polydispersity and mean hydrodynamic diameters ranging from 25 to 150 nm. Following intravenous injection, GPMs provided blood pool contrast for up to 24 h and improved the delineation of tumor margins via CT. Thus, GPM-enhanced CT imaging was used to guide radiation therapy delivered via a small animal radiation research platform. In combination with the radiosensitizing capabilities of gold, tumor-bearing mice exhibited a 1.7-fold improvement in the median survival time, compared with mice receiving radiation alone. It is envisioned that translation of these capabilities to human cancer patients could guide and enhance the efficacy of radiation therapy. PMID:24377302

  6. Gold-loaded polymeric micelles for computed tomography-guided radiation therapy treatment and radiosensitization.

    PubMed

    Al Zaki, Ajlan; Joh, Daniel; Cheng, Zhiliang; De Barros, André Luís Branco; Kao, Gary; Dorsey, Jay; Tsourkas, Andrew

    2014-01-28

    Gold nanoparticles (AuNPs) have generated interest as both imaging and therapeutic agents. AuNPs are attractive for imaging applications since they are nontoxic and provide nearly three times greater X-ray attenuation per unit weight than iodine. As therapeutic agents, AuNPs can sensitize tumor cells to ionizing radiation. To create a nanoplatform that could simultaneously exhibit long circulation times, achieve appreciable tumor accumulation, generate computed tomography (CT) image contrast, and serve as a radiosensitizer, gold-loaded polymeric micelles (GPMs) were prepared. Specifically, 1.9 nm AuNPs were encapsulated within the hydrophobic core of micelles formed with the amphiphilic diblock copolymer poly(ethylene glycol)-b-poly(ε-capralactone). GPMs were produced with low polydispersity and mean hydrodynamic diameters ranging from 25 to 150 nm. Following intravenous injection, GPMs provided blood pool contrast for up to 24 h and improved the delineation of tumor margins via CT. Thus, GPM-enhanced CT imaging was used to guide radiation therapy delivered via a small animal radiation research platform. In combination with the radiosensitizing capabilities of gold, tumor-bearing mice exhibited a 1.7-fold improvement in the median survival time, compared with mice receiving radiation alone. It is envisioned that translation of these capabilities to human cancer patients could guide and enhance the efficacy of radiation therapy. PMID:24377302

  7. Robust Thick Polymer Brushes Grafted from Gold Surfaces Using Bidentate Thiol-Based Atom-Transfer Radical Polymerization Initiators.

    PubMed

    Park, Chul Soon; Lee, Han Ju; Jamison, Andrew C; Lee, T Randall

    2016-03-01

    A new bromoisobutyrate-terminated alkanethiol, 16-(3,5-bis(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methylpropanoate (BMTBM), was designed as a bidentate adsorbate to form thermally stable bromoisobutyrate-terminated self-assembled monolayers (SAMs) on flat gold surfaces to conduct atom-transfer radical polymerizations (ATRPs). The monolayers derived from BMTBM were characterized by ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and compared to the monolayers formed from 16-mercaptohexadecyl 2-bromo-2-methylpropanoate (MBM), 16-(3-(mercaptomethyl)phenoxy)hexadecyl 2-bromo-2-methyl-propanoate (MTBM), and octadecanethiol (C18SH). In this study, although the monolayer derived from BMTBM was less densely packed than those derived from MBM and MTBM, the bidentate adsorbates demonstrated much higher thermal stability in solution-phase thermal desorption tests, owing to the "chelate effect". The enhanced stability of the BMTBM SAMs ensured the development of thick brushes of poly(methyl methacrylate) and polystyrene at elevated temperatures (60, 90, 105, and 120 °C). In contrast, SAMs derived from MBM and MTBM failed to grow polymer brushes at temperatures above 100 °C. PMID:26841087

  8. Radiolytic method of preparation of semiconductor assemblies supported on polymeric membranes

    NASA Astrophysics Data System (ADS)

    Haruvy, Y.; Gratzel, M.; Rajbenbach, L. A.

    Radiation induced grafting of hydrophilic acrylic monomers onto polymeric films and fabric has been employed to prepare supports for catalytic assemblies, which are highly permeable to water and low molecular weight solutes. Transition-metal-oxide semiconductor clusters embedded within the grafted membranes were formed by swelling the membranes with a solution of metal alkoxides followed by gradual hydrolysis. Photolytic methods have been employed to form Pt° clusters onto the semiconductor agregates. Kinetic aspects of the radiation induced grafting of the polymeric supports and the mechanistic features of the preparation of polymer-anchored TiO 2 clusters loaded with Pt° are described. The photocatalytic effectiveness of the TiO 2-Pt assemblies embedded in recoverable polymeric grids was demonstrated in hydrogen generation from aqueous solution and in the degradation of environmental pollutants.

  9. Effects of solvents on the radiation grafting reaction of vinyl compounds on poly (3-hydroxybutyrate)

    NASA Astrophysics Data System (ADS)

    Torres, Maykel González; Talavera, José Rogelio Rodríguez; Muñoz, Susana Vargas; Pérez, Manuel González; Castro, Ma. Pilar. Carreón.; Cortes, Jorge Cerna; Muñoz, Rodrigo Alonso Esparza

    2015-03-01

    Vinyl Acetate was grafted onto poly (3-hydroxybutyrate) by the simultaneous gamma irradiation method using different types of solvents and in bulk (solvent free), at 10 kGy and 1.62 kGy/h dose and dose rate respectively. Subsequent complete hydrolysis allowed the conversion of grafted chains from poly (vinyl acetate) to poly (vinyl alcohol). The aim of this study is to determine the effect of solvent through the estimation of the dependence of the degree of grafting with the choice of solvent, the calculation of the degree of crystallinity, and to study the biodegradation of the products. The results showed a greater degree of grafting in bulk, while the more suitable solvent was hexane. Characterization of the grafted copolymer indicated that crystallinity percentage decreased by an increase in grafting, while the biodegradability was promoted by the increment in poly (vinyl alcohol) grafted.

  10. Electrospun regenerated cellulose nanofibrous membranes surface-grafted with polymer chains/brushes via the atom transfer radical polymerization method for catalase immobilization.

    PubMed

    Feng, Quan; Hou, Dayin; Zhao, Yong; Xu, Tao; Menkhaus, Todd J; Fong, Hao

    2014-12-10

    In this study, an electrospun regenerated cellulose (RC) nanofibrous membrane with fiber diameters of ∼200-400 nm was prepared first; subsequently, 2-hydroxyethyl methacrylate (HEMA), 2-dimethylaminoethyl methacrylate (DMAEMA), and acrylic acid (AA) were selected as the monomers for surface grafting of polymer chains/brushes via the atom transfer radical polymerization (ATRP) method. Thereafter, four nanofibrous membranes (i.e., RC, RC-poly(HEMA), RC-poly(DMAEMA), and RC-poly(AA)) were explored as innovative supports for immobilization of an enzyme of bovine liver catalase (CAT). The amount/capacity, activity, stability, and reusability of immobilized catalase were evaluated, and the kinetic parameters (Vmax and Km) for immobilized and free catalase were determined. The results indicated that the respective amounts/capacities of immobilized catalase on RC-poly(HEMA) and RC-poly(DMAEMA) nanofibrous membranes reached 78 ± 3.5 and 67 ± 2.7 mg g(-1), which were considerably higher than the previously reported values. Meanwhile, compared to that of free CAT (i.e., 18 days), the half-life periods of RC-CAT, RC-poly(HEMA)-CAT, RC-poly(DMAEMA)-CAT, and RC-poly(AA)-CAT were 49, 58, 56, and 60 days, respectively, indicating that the storage stability of immobilized catalase was also significantly improved. Furthermore, the immobilized catalase exhibited substantially higher resistance to temperature variation (tested from 5 to 70 °C) and lower degree of sensitivity to pH value (tested from 4.0 and 10.0) than the free catalase. In particular, according to the kinetic parameters of Vmax and Km, the nanofibrous membranes of RC-poly(HEMA) (i.e., 5102 μmol mg(-1) min(-1) and 44.89 mM) and RC-poly(DMAEMA) (i.e., 4651 μmol mg(-1) min(-1) and 46.98 mM) had the most satisfactory biocompatibility with immobilized catalase. It was therefore concluded that the electrospun RC nanofibrous membranes surface-grafted with 3-dimensional nanolayers of polymer chains/brushes would be suitable/ideal as efficient supports for high-density and reusable enzyme immobilization. PMID:25396286

  11. Effects of γ-ray radiation grafting on aramid fibers and its composites

    NASA Astrophysics Data System (ADS)

    Zhang, Y. H.; Huang, Y. D.; Liu, L.; Cai, K. L.

    2008-03-01

    Armos fiber was modified by Co 60 γ-ray radiation in the different concentrations' mixtures of phenol-formaldehyde and ethanol. Interlaminar shear strength (ILSS) was examined to characterize the effects of the treatment upon the interfacial bonding properties of Armos fibers/epoxy resin composites. The results showed that the ILSS of the composite, whose fibers were treated by 500 kGy radiation in 1.5 wt% PF, was improved by 25.4%. Nanoindentation technique analysis showed that the nanohardnesses of the various phases (the fiber, the interface and the matrix) in the composite, whose fibers were treated, were correspondingly higher than those in the composite, whose fibers were untreated. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectrum confirmed the increase in the polar groups at the fibers' surface. Atomic force microscopy (AFM) results revealed that the surface of the fibers treated was rougher than that of the fibers untreated. The wettability of the fibers' surface was also enhanced by the treatment. The conclusion that γ-ray irradiation grafting significantly improved the surface properties of Armos fibers could be drawn.

  12. Application of radiation grafted media for lectin affinity separation and urease immobilization: A novel approach to tumor therapy and renal disease diagnosis

    NASA Astrophysics Data System (ADS)

    Müller-Schulte, D.; Daschek, W.

    1995-09-01

    Carriers modified by synergistic radiation grafting are used as affinity media for the separation of a lectin from a mistletoe extract. The grafted supports show distinctly superior properties when compared to conventional affinity media. The application of these carriers as urease immobilization support incorporated in a conductimetric bioreactor for urea analysis as potential diagnostic device in renal diseases is also described.

  13. Enhanced separation performance of PVDF/PVP-g-MMT nanocomposite ultrafiltration membrane based on the NVP-grafted polymerization modification of montmorillonite (MMT).

    PubMed

    Wang, Panpan; Ma, Jun; Wang, Zhenghui; Shi, Fengmei; Liu, Qianliang

    2012-03-13

    A novel hydrophilic nanocomposite additive (PVP-g-MMT), coupling of hydrophilic modifier, self-dispersant, and pore-forming agent (porogen), was synthesized by the surface modification of montmorillonite (MMT) with N-vinylpyrrolidone (NVP) via "grafting from" polymerization in the presence of H(2)O(2)-NH(3)·H(2)O as the initiator, and then the nanocomposite membrane of poly(vinylidene fluoride) (PVDF) and PVP-g-MMT was fabricated by wet phase inversion onto clean glass plates. The existence and dispersion of PVP-g-MMT had a great role on structures, morphologies, surface composition, and chemistry of the as-prepared nanocomposite membranes confirmed by varieties of spectroscopic and microscopic characterization techniques, all of which were the correlated functions of PVP-g-MMT content in casting solution. By using the dead-end filtration of protein aqueous solution, the performance of the membrane was evaluated. It was seen that all of the nanocomposite membranes showed obvious improvement of water flux and proper BSA rejection ratio, compared to the control PVDF membrane. Meanwhile, dynamic BSA fouling resistance and flux recovery properties were also greatly enhanced due to the changes of surface hydrophilicity and morphologies. All the experimental results indicated that the as-prepared PVDF nanocomposite membranes showed better separation performances than the control PVDF membrane. Hopefully, the demonstrated method of hydrophilic nanocomposite additive synthesis would be applied for commonly hydroxyl group-containing inorganic nanoparticles, which was favorable to fabricate hydrophilic nanoparticle-enhanced polymer membranes for water treatment. PMID:22376185

  14. Immobilization of antibodies and enzyme-labeled antibodies by radiation polymerization

    SciTech Connect

    Kumakura, M.; Kaetsu, I.; Suzuki, M.; Adachi, S.

    1983-04-01

    Immobilization of antibodies and enzyme-labeled antibodies by radiation polymerization at low temperatures was studied. The antibody activity of antibody was not affected by irradiation at an irradiation dose of below 8 MR and low temperatures. Immobilization of peroxidase-labeled anti-rabbit IgG goat IgG, anti-peroxidase, peroxidase, and anti-alpha-fetoprotein was carried out with hydrophilic and hydrophobic monomers. The activity of the immobilized enzyme-labeled antibody membranes varied with the thickness of the membranes and increased with decreasing membrane thickness. The activity of the immobilized antibody particles was varied by particle size. Immobilized anti-alpha-fetoprotein particles and membranes can be used for the assay of alpha-fetoprotein by the antigen-antibody reaction, such as a solid-phase sandwich method with high sensitivity.

  15. Characterization of Network Structure of Polyacrylamide Based Hydrogels Prepared By Radiation Induced Polymerization

    SciTech Connect

    Mahmudi, Naim; Sen, Murat; Gueven, Olgun; Rendevski, Stojan

    2007-04-23

    In this study network structure of polyacrylamide based hydrogels prepared by radiation induced polymerization has been investigated. Polyacrylamide based hydrogels in the rod form were prepared by copolymerization of acrylamide(AAm) with hydroxyl ethyl methacrylate(HEMA) and methyl acrylamide(MAAm) in the presence of cross-linking agent and water by gamma rays at ambient temperature. Molecular weight between cross-links and effective cross-link density of hydrogels were calculated from swelling as well as shear modulus data obtained from compression tests. The results have shown that simple compression analyses can be used for the determination of effective cross-link density of hydrogels without any need to some polymer-solvent based parameters as in the case of swelling based determinations. Diffusion of water into hydrogels was examined by analyzing water absorption kinetics and the effect of network, structure on the diffusion type and coefficient was discussed.

  16. Controlled release of multi-component cytotoxic agents from radiation polymerized composites.

    PubMed

    Kaetsu, I; Yoshida, M; Kumakura, M; Yamada, A; Sakurai, Y

    1980-01-01

    Multi-component cytotoxic (anticancer) agents such as mitomycin C (MMC), adryamycin (ADM) and 1-(2-tetrahydrofuryl-5-fluorouracil) (FT-207), were entrapped in a single common composite by radiation-induced polymerization of glass-forming monomers in the presence of polymers. The release profiles of each cytotoxic agent were controlled by the contents and compositions of three cytotoxic agents in the matrix. The release rates of each cytotoxic agent were retarded by addition of an adsorbent and accelerated by addition of a pore-making agent. The release fom the common matrix of a cytotoxic agent and its promoter which have markedly different molecular weights [e.g. MMC and urokinase (UK)] was also investigated. A double entrapping method was successfully used for controlled release in such cases. In conclusion it was found that the release profiles of multi-components in a single matrix could be controlled by using these techniques. PMID:7470547

  17. Hydrolysis behavior of regenerated celluloses with different degree of polymerization under microwave radiation.

    PubMed

    Ni, Jinping; Teng, Na; Chen, Haizhen; Wang, Jinggang; Zhu, Jin; Na, Haining

    2015-09-01

    This work studied the hydrolysis behavior of regenerated celluloses (RCs) with different degree of polymerization (DP) by using the catalyst of dilute acid under microwave radiation. Results showed that the DP had a considerable influence on hydrolysis of cellulose. The reactivity of RCs was significantly improved when DP was lower than 51. The highest sugar yield of 59.2% was achieved from RC with lowest DP of 23 at 160 °C for 15 min. But the lowest yield of 32.6% was obtained when RC with highest DP of 132 was used. Recrystallization of cellulose was found to hinder the further hydrolysis particularly with the high DP. The effect of recrystallization can be reduced by the decrease of DP of RCs. This research demonstrates that the DP of RCs plays a crucial role on hydrolysis and it provides a preliminary guide based on DP to find a suitable pretreatment method for cellulose hydrolysis. PMID:25997012

  18. A study of ethanol production of yeast cells immobolized with polymer carrier produced by radiation polymerization

    NASA Astrophysics Data System (ADS)

    Zhaoxin, Lu; Fujimura, Takashi

    1993-10-01

    Polymer carriers, poly(hydroxyethyl acrylate(HEA)-methoxy polyethylene glycol methylacrylate (M-23G)) and poly (hydroxyethyl accrylate(HEA)-glycidyl methlacrylate(GMA)) using for immobilization of yeast cells were prepared by radiation polymerization at low temperature. Yeast cells were immobilized through adhesion and multiplication of yeast cells themselves. The ethanol productivity of immobilized yeast cells with these carriers was related to the monomer composition of polymers and the optimum monomer composition was 20% : 10% in poly(HEA-M-23G) and 17%: 6% in poly(HEA-GMA). In this case, the ethanol productivity of immobilized yeast cells was 29mg/ml/h which was about 4 times that of cells in free system. The relationship between the activity of immobilized yeast cells and the water content of polymer carrier were also discussed.

  19. Synthesis of CO2/N2-triggered reversible stability-controllable poly(2-(diethylamino)ethyl methacrylate)-grafted-AuNPs by surface-initiated atom transfer radical polymerization.

    PubMed

    Kitayama, Yukiya; Takeuchi, Toshifumi

    2014-10-28

    CO2/N2-triggered stability-controllable gold nanoparticles (AuNPs) grafted with poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) layers (PDEAEMA-g-AuNPs) were synthesized by the surface-initiated atom transfer radical polymerization of DEAEMA with AuNPs bearing the bis[2-(2-bromoisobutyryloxy)undecyl] layer (grafting from method). Extension of the PDEAEMA chain length increased the stability of the PDEAEMA-g-AuNPs in CO2-bubbled water because of the electrosteric repulsion of the protonated PDEAEMA layer. The chain-length-dependent stability of PDEAEMA-g-AuNPs was confirmed by DLS and UV-vis spectra by using the localized surface plasmon resonance property of the AuNPs, where the extinction wavelength was shifted toward shorter wavelength with increasing PDEAEMA chain length. The reversible stability change with the gas stimuli of CO2/N2 was also successfully demonstrated. Finally, the transfer across the immiscible interface between water and organic solvent was successfully demonstrated by N2-triggered insolubilization of PDEAEMA layer on AuNPs in the aqueous phase, leading to the successful collection of AuNPs using organic solvent from the aqueous phase. Our "grafting from" method of reversible stability-controllable AuNPs can be applied to develop advanced materials such as reusable optical AuNP-based nanosensors because the molecular recognition layer can be constructed by two-step polymerization. PMID:25268967

  20. Modification of polyethylene films by radiation grafting of glycidyl methacrylate and immobilization of ?-cyclodextrin

    NASA Astrophysics Data System (ADS)

    Nava-Ortiz, C. A. B.; Burillo, G.; Bucio, E.; Alvarez-Lorenzo, C.

    2009-01-01

    Glycidyl methacrylate was grafted onto polyethylene films using a preirradiation method with ? rays. The effect of absorbed dose, monomer concentration, and reaction time on the degree of grafting was determined. The grafted samples were verified by FTIR-ATR spectroscopy. ?-Cyclodextrin was immobilized onto polypropylene modified with glycidyl methacrylate, and the ability of the cavities of ?-cyclodextrin to form inclusion complexes was demonstrated using the typically organic compound approach with m-toluic acid (3-MBA) as a probe.

  1. Synthesis, characterization, and morphology study of poly(acrylamide-co-acrylic acid)-grafted-poly(styrene-co-methyl methacrylate) "raspberry"-shape like structure microgels by pre-emulsified semi-batch emulsion polymerization.

    PubMed

    Ramli, Ros Azlinawati; Hashim, Shahrir; Laftah, Waham Ashaier

    2013-02-01

    A novel microgels were polymerized using styrene (St), methyl methacrylate (MMA), acrylamide (AAm), and acrylic acid (AAc) monomers in the presence of N,N'-methylenebisacrylamide (MBA) cross-linker. Pre-emulsified monomer was first prepared followed by polymerizing monomers using semi-batch emulsion polymerization. Fourier Transform Infrared Spectroscopy (FTIR) and (1)H Nuclear Magnetic Resonance (NMR) were used to determine the chemical structure and to indentify the related functional group. Grafting and cross-linking of poly(acrylamide-co-acrilic acid)-grafted-poly(styrene-co-methyl methacrylate) [poly(AAm-co-AAc)-g-poly(St-co-MMA)] microgels are approved by the disappearance of band at 1300 cm(-1), 1200 cm(-1) and 1163 cm(-1) of FTIR spectrum and the appearance of CH peaks at 5.5-5.7 ppm in (1)H NMR spectrum. Scanning Electron Microscope (SEM) images indicated that poly(St-co-MMA) particle was lobed morphology coated by cross-linked poly(AAm-co-AAc) shell. Furthermore, SEM results revealed that poly(AAm-co-AAc)-g-poly(St-co-MMA) is composite particle that consist of "raspberry"-shape like structure core. Internal structures of the microgels showed homogeneous network of pores, an extensive interconnection among pores, thicker pore walls, and open network structures. Water absorbency test indicated that the sample with particle size 0.43 μm had lower equilibrium water content, % than the sample with particle size 7.39 μm. PMID:23123033

  2. Radiation grafting of acrylic and methacrylic acid to cellulose fibers to impart high water sorbency

    SciTech Connect

    Zahran, A.H.; Williams, J.L.; Stannett, V.T.

    1980-04-01

    Acrylic and methacrylic acids have been directly grafted to rayon and cotton using the preirradiation technique with /sup 60/ Co gamma rays. The rate of grafting increased with increasing temperature and monomer concentration, as did the final degree of grafting. The amount and rate of grafting also increased with the total irradiation dose but tended to level off at higher doses, in agreement with the leveling off of the radical content reported previously. Methacrylic acid grafted more and faster than acrylic acid to both rayon and cotton. Methacrylic acid grafted more with rayon than cotton, but acrylic acid gave somewhat similar yields with both fibers. The water abosrbency of the grafted fibers depended strongly on their posttreatment. Decrystallizing with 70% zinc chloride or with hot sodium hydroxidy developed supersorbency. The two treatments in succession, respectively, gave the highest values. Metacrylic acid brought about less sorbency than the corrsponding acrylic acid grafts. Useful levels of grafting and supersorbency could be readily and practically achieved by the methods described.

  3. Preparation and characterization of glycidyl methacrylate grafted 4-amino-1,2,4-triazole modified nonwoven fiber adsorbent for environmental application

    NASA Astrophysics Data System (ADS)

    Kavaklı, Cengiz; Akkaş Kavaklı, Pınar; Güven, Olgun

    2014-01-01

    A novel 4-amino-1,2,4-triazole (ATZ) containing nonwoven fiber was prepared by means of radiation induced graft polymerization. For this purpose, glycidyl methacrylate (GMA) was grafted onto polyethylene coated polypropylene nonwoven fibers (NWF) in emulsion medium by using radiation induced graft polymerization. Grafting conditions were optimized and epoxy groups of grafted GMA were then modified with ATZ. Optimum conditions for modification were conducted in different solvents i.e. water and dioxane/water mixture at different amino triazole concentrations (5%, 10%, 20% (w/w)). Maximum modification was obtained in 10% (w/w) ATZ solution in dioxane/water mixture as a solvent at 80 °C. Prepared nonwoven fibers were characterized by FTIR and thermal analysis techniques.

  4. Pre-irradiation-induced graft reaction of maleic anhydride onto polypropylene

    NASA Astrophysics Data System (ADS)

    Tan, X. M.; Xu, Y. S.; Wang, C. L.

    2006-09-01

    The radiation induced graft polymerization is a well-known method to obtain new materials. Until recently, only conventional radiation sources, such as Co-60 and electron beams, were used. Moreover, part of the damage induced in polymers by heavy ions can produce active sites (peroxides and hydroperoxides) that are useful to initiate grafting reactions. Maleic anhydride (MAH) was grafted onto polypropylene (PP) wax with a number-average molecular weight (Mn) of 8000 by gamma pre-irradiation technique. Effects of total dose, monomer concentration, reaction time, and temperature on percentage of grafting are studied in detail. It is shown that the optimum conditions for grafting are temperature of 70 degrees C and total dose of 14.4 kGy. PP-g-MAH is characterized by infrared spectrum. Differential scanning calorimetry shows that the compatibility of PP-g-MAH is better than that of PP.

  5. Radiation-grafting of N-vinylimidazole onto silicone rubber for antimicrobial properties

    NASA Astrophysics Data System (ADS)

    Meléndez-Ortiz, H. Iván; Alvarez-Lorenzo, Carmen; Burillo, Guillermina; Magariños, Beatriz; Concheiro, Angel; Bucio, Emilio

    2015-05-01

    Poly(N-vinylimidazole) (PVIm) was grafted numbers onto silicone rubber (SR) with the aim of providing antimicrobial properties. The grafting was carried out by means of gamma rays using the direct method. The influence on the grafting yield of absorbed dose, monomer concentration, addition of FeSO4 salt, composition and type of solvent (H2O, MeOH, THF, and acetone) was investigated. Grafts onto SR between 10% and 90% were obtained at doses from 20 to 100 kGy and a dose rate 10.9 kGy h-1; grafting yield increased with monomer concentration and dose. The new graft copolymers were confirmed by Fourier transform infrared spectroscopy (FT-IR). Differential scanning calorimeter (DSC) showed glass transition at 149 and 159 °C for 38% and 88% grafting respectively. Thermogravimetry analysis (TGA) presented two decomposition temperatures for SR-g-VIm at 380 (PVIm) and 440 °C (SR). SR-g-VIm showed antibacterial activity against Pseudomonas aeruginosa.

  6. Radiation grafting of acrylamide onto starch-filled low density polyethylene

    NASA Astrophysics Data System (ADS)

    Bagheri, Rouhallah; Naimian, Franak; Sheikh, Nassrin

    1997-04-01

    Acrylamide (AAm) was grafted on the surface of starch-filled low density polyethylene (SLDPE) and low density polyethylene (LDPE) films by the mutual irradiation technique at doses from 0.75 to 5 kGy. The effect of dose, solvents and dihydroxybenzoquinone on the degree of grafting was studied by Fourier transform infrared spectroscopy and the weight measurement method of extracted films at a constant monomer concentration (10% w/w). An ultraviolet spectrophotometer was also used to elucidate the results of the above methods. Grafting on SLDPE and LDPE samples reaches a maximum followed by a slight decrease with increasing dose. A higher degree of grafting was obtained on SLDPE samples compared with that on LDPE. An induction period was observed in the case of the samples prepared in tetrahdyrfuran (THF) as the solvent compared with those in chloroform. Addition of benzene to chloroform and THF (50% v/v) accelerates the rate of AAm grafting on the samples. Dihydroxybenzoquinone inhibits the grafting reactions of the samples especially in the THF solutions. The water uptake measurement of the samples correlates with the degree of grafting.

  7. Comparative studies on PADC polymeric detector treated by gamma radiation and Ar ion beam

    NASA Astrophysics Data System (ADS)

    El-Saftawy, A. A.; Abdel Reheem, A. M.; Kandil, S. A.; Abd El Aal, S. A.; Salama, S.

    2016-05-01

    In the present study, a comparative analysis and evaluation of the induced defects in polyallyl diglycol carbonate (PADC) polymeric detector exposed to Ar+ and gamma radiation were made. To get insight into the structure defects due to irradiation, X-ray diffraction (XRD) technique was employed. The PADC surface structure changed after irradiation due to the reduction in the surface crystalline structure and the formation of disordered systems. Also, surface morphology changes were traced using scanning electron microscopy (SEM) and showed minor surface irregularities after gamma irradiation and large changes upon Ar+ irradiation. Additionally, micro-hardness and friction coefficient of the irradiated samples were investigated and found to increase after irradiation. UV-vis spectroscopy was used to estimate the optical band gap energy which considered as the basis for calculating the number of conjugated carbon atoms responsible for the blackening effect and color changes took place over the PADC surface. It was found that as the applied dose increased, the band gap decreased and the number of carbon clusters get larger. The refractive index and the dispersion parameters for the studied polymer were calculated and discussed. Also, the induced defects on the polymer surface which serve as a non-radiative centers resulting in reduced photoluminescence (PL) intensity. For nearly all the measured parameters, gamma irradiated samples showed a significant changes compared to that induced by ions. But, low energy Ar+ prove efficiency in controlling surface properties of PADC polymer without affecting its sensitive bulk properties, besides that the obtained results are reasonable and comparable to that induced by gamma radiation.

  8. Determining the molecular origin of radiation damage/enhancement in electro-optic polymeric materials through polarized light microscopy

    NASA Astrophysics Data System (ADS)

    Perez-Moreno, Javier

    2014-09-01

    Previous studies on the radiation effects upon polymer and polymer-based photonic materials suggest that the radiation resistance of the material is heavily dependent on the choice of polymer-host and guest-chromophore. The best results to date have been achieved with electro optic polymeric materials based on CLD1 doped in APC, which has resulted in improved performance at the device level upon gamma-ray irradiation at moderate doses. Still, our understanding of the physical mechanisms behind the enhancement of the performance is unclear. In this paper, we discuss how polarized light microscopy could be used as a means to quantify the effect of the different physical parameters that influence the optical response of electro-optic polymeric thin film samples.

  9. Radiation grafting of oligo(ethylene glycol) ethyl ether methacrylate on polypropylene

    NASA Astrophysics Data System (ADS)

    Komasa, Justyna; Miłek, Andrzej; Ulański, Piotr; Rosiak, Janusz M.

    2014-01-01

    Oligo(ethylene glycol) ethyl ether methacrylate (OEGMA) can be grafted onto polypropylene (PP) films by post-irradiation grafting, forming a thermosensitive polymer layer, as indicated by FT-IR and contact angle measurements. In the first step, PP foils are irradiated by electron beam (5.5 kGy/min, up to 300 kGy) in the presence of air. Subsequently, the irradiated foils react with the monomer in oxygen-free solutions in isopropanol (up to 2 M of monomer) at 70 °C. Degree of grafting of OEGMA can be controlled by proper selection of absorbed dose, monomer concentration and reaction time. This work is a part of a broader project on thermosensitive materials facilitating cell growth and detachment for optimizing cell layer engineering techniques in the treatment of burn wounds.

  10. Polymeric Materials With Additives for Durability and Radiation Shielding in Space

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard

    2011-01-01

    Polymeric materials are attractive for use in space structures because of their light weight and high strength In addition, polymers are made of elements with low atomic numbers (Z), primarily carbon (C), hydrogen (H), oxygen (0), and nitrogen (N) which provide the best shielding from galactic cosmic rays (GCR) (ref. 1). Galactic cosmic rays are composed primarily of nuclei (i.e., fully ionized atoms) plus a contribution of about 2% from electrons and positrons. There is a small but significant component of GCR particles with high charge (Z > 10) and high energy (E >100 GeV) (ref. 2). These so-called HZE particles comprise only 1 to 2% of the cosmic ray fluence but they interact with very high specific ionization and contribute 50% of the long- term dose to humans. The best shield for this radiation would be liquid hydrogen, which is not feasible. For this reason, hydrogen-containing polymers make the most effective practical shields. Moreover, neutrons are formed in the interactions of GCR particles with materials. Neutrons can only lose energy by collisions or reactions with a nucleus since they are uncharged. This is a process that is much less probable than the Coulombic interactions of charged particles. Thus, neutrons migrate far from the site of the reaction in which they were formed. This increases the probability of neutrons reaching humans or electronic equipment. Fast neutrons (> 1 MeV) can interact with silicon chips in electronic equipment resulting in the production of recoil ions which can cause single event upsets (SEU) in sensitive components (ref. 3). Neutrons lose energy most effectively by elastic collisions with light atoms, particularly hydrogen atoms. Therefore, hydrogen-containing polymers are not only effective in interacting with GCR particles; they are also effective in reducing the energy of the neutrons formed in the interactions.

  11. A gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters

    NASA Astrophysics Data System (ADS)

    Babic, S.; Park, Y. S.; Schreiner, L. J.

    2004-01-01

    In this presentation we show results of investigations on gelatin-free dosimeters containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide (named Aqueous Polyacrylamide, APA, dosimeters). The dosimeters were prepared with three different total monomer concentrations (2, 6, and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all three dosimeters, show a continuous degree of polymerization over the range of dose 0.5 - 25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of cross-linked polymer formed at each dose. This model may be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

  12. Gamma-ray co-irradiation induced graft polymerization of NVP and SSS onto polypropylene non-woven fabric and its blood compatibility

    NASA Astrophysics Data System (ADS)

    Li, Rong; Wang, Hengdong; Wang, Wenfeng; Ye, Yin

    2013-10-01

    Sodium styrenesulfonate was grafted onto PPNWF via γ-ray co-irradiation method with the existence of N-vinyl-2-pyrrolidone. The effect of absorbed dose, dose rate and concentration of binary monomer on the degree of grafting was investigated. The surface chemical change was characterized by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The wettability was characterized through the measurement of adsorption percentage of water and phosphate buffer solution (PBS). The result demonstrated that the grafted poly(NVP-co-SSS) chains can improve the hydrophilicity of PPNWF. Furthermore, the modified PPNWF has good blood compatibility, such as low hemolysis rate, low platelet adhesion and effectively extending the blood coagulation times. Consequently, hydrophilicity and hemocompatibility of PPNWF were greatly enhanced by the immobilization of poly(NVP-co-SSS) chains.

  13. Radiation-induced reduction-polymerization route for the synthesis of PEDOT conducting polymers

    NASA Astrophysics Data System (ADS)

    Cui, Zhenpeng; Coletta, Cecilia; Rebois, Rolando; Baiz, Sarah; Gervais, Matthieu; Goubard, Fabrice; Aubert, Pierre-Henri; Dazzi, Alexandre; Remita, Samy

    2016-02-01

    Synthesis of conducting poly(3,4-ethylenedioxythiophene), PEDOT, is achieved through an original reduction-polymerization route: γ-radiolysis of aqueous solutions containing EDOT monomers under N2 atmosphere. According to UV-vis absorption spectrophotometry and ATR-FTIR spectroscopy, reduction of EDOT is initiated by hydrated electrons produced by water radiolysis and leads to PEDOT polymers through coupling reactions. The morphology of PEDOT is characterized by Cryo- TEM microscopy in aqueous solution and by SEM after deposition. In an original way, high resolution AFM microscopy, coupled with infrared nanospectroscopy, is used to probe the local chemical composition of PEDOT nanostructures. The results demonstrate that spherical self-assembled PEDOT nanostructures are formed. TGA analysis and four point probe measurements demonstrate that thermal stability and electrical conductivity of PEDOT polymers obtained by the present original reduction-polymerization method are close to those of PEDOT we previously prepared by radiolysis according to an oxidation-polymerization route.

  14. Evaluation of Thermal Control Coatings and Polymeric Materials Exposed to Ground Simulated Atomic Oxygen and Vacuum Ultraviolet Radiation

    NASA Technical Reports Server (NTRS)

    Kamenetzky, R. R.; Vaughn, J. A.; Finckenor, M. M.; Linton, R. C.

    1995-01-01

    Numerous thermal control and polymeric samples with potential International Space Station applications were evaluated for atomic oxygen and vacuum ultraviolet radiation effects in the Princeton Plasma Physics Laboratory 5 eV Neutral Atomic Oxygen Facility and in the MSFC Atomic Oxygen Drift Tube System. Included in this study were samples of various anodized aluminum samples, ceramic paints, polymeric materials, and beta cloth, a Teflon-impregnated fiberglass cloth. Aluminum anodizations tested were black duranodic, chromic acid anodize, and sulfuric acid anodize. Paint samples consisted of an inorganic glassy black paint and Z-93 white paint made with the original PS7 binder and the new K2130 binder. Polymeric samples evaluated included bulk Halar, bulk PEEK, and silverized FEP Teflon. Aluminized and nonaluminized Chemfab 250 beta cloth were also exposed. Samples were evaluated for changes in mass, thickness, solar absorptance, and infrared emittance. In addition to material effects, an investigation was made comparing diffuse reflectance/solar absorptance measurements made using a Beckman DK2 spectroreflectometer and like measurements made using an AZ Technology-developed laboratory portable spectroreflectometer.

  15. Bone Grafts

    MedlinePlus

    A bone graft transplants bone tissue. Surgeons use bone grafts to repair and rebuild diseased bones in your hips, knees, ... fractures or cancers. Once your body accepts the bone graft, it provides a framework for growth of new, ...

  16. Mechanical properties of tough hydrogels synthesized with a facile simultaneous radiation polymerization and cross-linking method

    NASA Astrophysics Data System (ADS)

    Jiang, Fangzhi; Wang, Xuezhen; He, Changcheng; Saricilar, Sureyya; Wang, Huiliang

    2015-01-01

    Radiation-induced polymerization and cross-linking method has been applied to hydrogel preparations for decades, but less attention has been paid to the mechanical properties of the hydrogels. In this work, we provide a systematic study on the mechanical properties of hydrogels synthesized with the simultaneous radiation polymerization and cross-linking method. The prepared polyacrylamide (PAAm) had very good mechanical properties, namely high compressive strengths (several to more than 10 MPa), high tensile strengths (up to 260 kPa), high fracture strains (up to 12) and high fracture energies (10-160 J/m2). Absorbed dose and monomer concentration were the two important factors affecting the mechanical properties of the gels. The compressive strength and elastic modulus of the gels increased with increasing absorbed dose and monomer concentration, while the tensile strength, fracture strain and fracture energy of the gels decreased with increasing absorbed dose. The gels also showed excellent elastic recovery property, as indicated by the low stress-strain hysteresis ratios in cyclic tensile tests as well as the small loss factors measured with dynamic mechanical analysis (DMA).

  17. Development of novel hydrogels by modification of sterculia gum through radiation cross-linking polymerization for use in drug delivery

    NASA Astrophysics Data System (ADS)

    Singh, Baljit; Vashishtha, Manu

    2008-05-01

    In order to modify the sterculia gum polysaccharide, to develop the hydrogels meant for the drug delivery, we have prepared sterculia gum, 2-hydroxyethylmethacrylate (HEMA) and acrylic acid (AAc) based hydrogels by radiation-induced crosslinking polymerization. Polymeric networks (hydrogels) thus formed were characterized with SEMs, FTIR,TGA and swelling studies which were carried out as a function monomers concentration, radiation dose, amount of sterculia contents in the polymer matrix and nature of the swelling medium. This paper discusses the swelling kinetics of the hydrogels and release dynamics of anti-diarrhea model drug ornidazole from the hydrogels to evaluation of swelling and drug release mechanism. Diffusion exponent 'n' have 0.73, 0.56 and 0.61 values and gel characteristic constant 'k' have 1.28 × 10-2, 2.95 × 10-2 and 2.14 × 10-2 values in distilled water, pH 2.2 buffer and pH 7.4 buffer. The release of drug from the polymer matrix occurred through non-Fickian diffusion mechanism. The values for the late time diffusion coefficients have been lower than the values of initial and average diffusion coefficients. It reflects that in the initial stages rate of release of drug from polymer matrix was higher as compared to the late stages, it means after certain time the drug release occurred in controlled manner.

  18. Surface-initiated atom transfer radical polymerization of polyamine grafting from magnetic iron oxide submicroparticles for high adsorption capacity of cadmium in aqueous solution.

    PubMed

    Liu, Qingyang; Ji, Zhongxing; Bei, Yiling

    2013-03-15

    Chemical modification of magnetic submicroparticles (MSPs) with functional polymers using controlled/living radical polymerization method has recently gained a great deal of attentions because of the potential applications to water treatment. In this work, we demonstrated an efficient method for poly(glycidyl methacrylate) (pGMA) modification of MSPs, by surface-initiated atom transfer radical polymerization method, and then, the particles were actually modified by triethylenetetramine through epoxy groups of pGMA to form polyamine/MSPs. The material was characterized using infrared spectroscopy, thermo gravimetric analyzer, transmission electron microscopic, gel permeation chromatography, and vibrating sample magnetometer. Sorption of Cd(II) to polyamine/MSPs reached equilibrium in ~100 min and agreed well to the Freundlich isotherm equation with maximum adsorption capacity of 71.3 mg g(-1) for the 500 mg L(-1) Cd(II) aqueous solution at neutral pH. PMID:23273544

  19. Chemically grafted polymeric filters for chemical sensors: Hyperbranched poly(acrylic acid) films incorporating {Beta}-cyclodextrin receptors and amine-functionalized filter layers

    SciTech Connect

    Dermody, D.L.; Peez, R.F.; Bergbreiter, D.E.; Crooks, R.M.

    1999-02-02

    The authors report a new molecular-filter approach for enhancing the selectivity of chemical sensors. Specifically, they describe electrochemical sensors prepared from Au electrodes coated with {beta}-cyclodextrin-functionalized, hyperbranched poly(acrylic acid)(PAA) films capped with a chemically grafted, ultrathin polyamine layer. The hyperbranched PAA film is a highly functionalized framework for covalently binding the {beta}-cyclodextrin molecular receptors. The thin, grafted polyamine overlayer acts as a pH-sensitive molecular filter that selectively passes suitably charged analytes. Poly(amidoamine) dendrimers or poly-D-lysine is used as 10--15-nm-thick filter layers. The results show that at low pH, when the polyamines are fully protonated, positively charged redox probe molecules, such as benzyl viologen (BV), do not permeate the filter layer. However, at high pH, when the filter layer is uncharged, BV penetrates the filter layer and is reduced at the electrode. The opposite pH dependence is observed for negatively charged redox molecules such as anthraquinone-2-sulfonate (AQS). Both BV and AQS specifically interact with the {beta}-cyclodextrin receptors underlying the polyamine filter layers.

  20. Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes

    PubMed Central

    Chenette, Heather C.S.; Robinson, Julie R.; Hobley, Eboni; Husson, Scott M.

    2012-01-01

    This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

  1. Development of high-productivity, strong cation-exchange adsorbers for protein capture by graft polymerization from membranes with different pore sizes.

    PubMed

    Chenette, Heather C S; Robinson, Julie R; Hobley, Eboni; Husson, Scott M

    2012-12-15

    This paper describes the surface modification of macroporous membranes using ATRP (atom transfer radical polymerization) to create cation-exchange adsorbers with high protein binding capacity at high product throughput. The work is motivated by the need for a more economical and rapid capture step in downstream processing of protein therapeutics. Membranes with three reported nominal pore sizes (0.2, 0.45, 1.0 μm) were modified with poly(3-sulfopropyl methacrylate, potassium salt) tentacles, to create a high density of protein binding sites. A special formulation was used in which the monomer was protected by a crown ether to enable surface-initiated ATRP of this cationic polyelectrolyte. Success with modification was supported by chemical analysis using Fourier-transform infrared spectroscopy and indirectly by measurement of pure water flux as a function of polymerization time. Uniformity of modification within the membranes was visualized with confocal laser scanning microscopy. Static and dynamic binding capacities were measured using lysozyme protein to allow comparisons with reported performance data for commercial cation-exchange materials. Dynamic binding capacities were measured for flow rates ranging from 13 to 109 column volumes (CV)/min. Results show that this unique ATRP formulation can be used to fabricate cation-exchange membrane adsorbers with dynamic binding capacities as high as 70 mg/mL at a throughput of 100 CV/min and unprecedented productivity of 300 mg/mL/min. PMID:23175597

  2. Characterization of radiation-modified polymeric sorbents as materials for chromatography

    SciTech Connect

    Starchinin, A.Yu.; Ivanova, N.V.; Zibarev, P.V.

    1995-05-01

    Porous polymeric sorbents are widely used as column-packing materials in different versions of chromatography and as sorbents for preconcentrating organic trace impurities from environmental samples. It is generally agreed that future progress in this line involves the preparation of new thermostable polymeric sorbents with polar functional groups, a large surface area, and intermediate pore size. However, many of the functional groups cannot be introduced into the macromolecular structure immediately during synthesis. Furthermore, copolymerization often proceeds with a low extent of reaction; therefore, the reaction-produced materials are not very thermostable. Because of this, the elaboration of new methods for the purposeful modification of already-prepared porous polymers to endow them with the required structural and sorption properties and to extend the range of their practical implementation is particularly promising. This work is devoted to the possibility of using previously prepared modified porous sorbents for the gas-chromatographic separation of polar organic compounds and for the preconcentration of trace impurities or organic compounds from the air.

  3. Grafting of Methacrylonitrile and Ethyl Methacrylate onto Jute Fibre: Physico-chemical Characteristics of Grafted Jute

    NASA Astrophysics Data System (ADS)

    Mondal, Md. Ibrahim H.; Islam Farouqui, Faisul; Abu Hanif, Md.; Shafiur Rahman, G. M.; Asadul Hoque, Md.

    2005-10-01

    Modification of bleached jute fibre was done by graft co-polymerization with vinyl monomers e.g. methacrylonitrile and ethyl methacrylate, in aqueous medium using H2O2-Na2S2O3 as redox initiators. To make the process efficient, the optimized polymerization condition was established. The maximum percent grafting and grafting efficiency obtained at optimum grafting condition were 11.3 and 20.4% for MAN, respectively and that of 17.6 and 27.5% for EMA. Modification of bleached jute fibre with MAN and EMA reduced the loss in breaking strength and the yellowing on exposure to sunlight in air.

  4. Investigation of space radiation effects in polymeric film-forming materials

    NASA Technical Reports Server (NTRS)

    Giori, C.; Yamauchi, T.; Jarke, F.

    1975-01-01

    The literature search in the field of ultraviolet radiation effects that was conducted during the previous program, Contract No. NAS1-12549, has been expanded to include the effects of charged particle radiation and high energy electromagnetic radiation. The literature from 1958 to 1969 was searched manually, while the literature from 1969 to present was searched by using a computerized keyword system. The information generated from this search was utilized for the design of an experimental program aimed at the development of materials with improved resistance to the vacuum-radiation environment of space. Preliminary irradiation experiments were performed which indicate that the approaches and criteria employed are very promising and may provide a solution to the challenging problem of polymer stability to combined ultraviolet/high energy radiation.

  5. SYNTHESIS AND IN VITRO CHARACTERIZATION OF HYDROXYPROPYL METHYLCELLULOSE-GRAFT-POLY (ACRYLIC ACID/2-ACRYLAMIDO-2-METHYL-1-PROPANESULFONIC ACID) POLYMERIC NETWORK FOR CONTROLLED RELEASE OF CAPTOPRIL.

    PubMed

    Furqan Muhammad, Iqbal; Mahmood, Ahmad; Aysha, Rashid

    2016-01-01

    A super-absorbent hydrogel was developed by crosslinking of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and acrylic acid with hydroxypropyl methylcellulose (HPMC) for controlled release drug delivery of captopril, a well known antihypertensive drug. Acrylic acid and AMPS were polymerized and crosslinked with HPMC by free radical polymerization, a widely used chemical crosslinking method. N,N'-methylenebisacrylamide (MBA) and potassium persulfate (KPS) were added as cross-linker and initiator, respectively. The hydrogel formulation was loaded with captopril (as model drug). The concentration of captopril was monitored at 205 nm using UV spectrophotometer. Equilibrium swelling ratio was determined at pH 2, 4.5 and 7.4 to evaluate the pH responsiveness of the formed hydrogel. The super-absorbent hydrogels were evaluated by FTIR, SEM, XRD, and thermal analysis (DSC and TGA). The formation of new copolymeric network was determined by FTIR, XRD, TGA and DSC analysis. The hydrogel formulations with acrylic acid and AMPS ratio of 4: 1 and lower amounts of crosslinker had shown maximum swelling. Moreover, higher release rate of captopril was observed at pH 7.4 than at pH 2, because of more swelling capacity of copolymer with increasing pH of the aqueous medium. The present research work confirms the development of a stable hydrogel comprising of HPMC with acrylic acid and AMPS. The prepared hydrogels exhibited pH sensitive behav-ior. This superabsorbent composite prepared could be a successful drug carrier for treating hypertension. PMID:27008813

  6. Folate-Modified Poly(malic acid) Graft Polymeric Nanoparticles for Targeted Delivery of Doxorubicin: Synthesis, Characterization and Folate Receptor Expressed Cell Specificity.

    PubMed

    Yang, Yang; Li, Ning; Nie, Yu; Sheng, Mingming; Yue, Dong; Wang, Gang; Tang, James Z; Gu, Zhongwei

    2015-09-01

    A novel amphiphilic biodegradable cholesterol and poly(ethylene glycol)-folate grafted poly(?,?-malic acid) (PMA-g-Chol/PEG-FA) was synthesized and characterized as self-assembled nanoparticles for targeted delivery of doxorubicin (DOX). The nanoparticles showed extremely low critical aggregation concentrations (CAC), appropriate zeta potential, narrow size distribution, good stability in serum conditions and negligible toxicity. After encapsulation'of DOX, PMA-g-Chol/PEG-FA nanoparticles showed significantly reduced cell viability (up to 30% for Hela and 27% for 4T1 cells) compared with the non-targeted ones on carcinoma cells with different levels of folate receptor (FR) expression. While no difference was detected on HEK293 cells (FR receptor negative) between the two nanoparticles. Addition of extra free folate obviously decreased the cellular mortality and inhibited the cellular uptake of targeted nanoparticles. In the Hela/HEK293 co-culture model, folate conjugated nanoparticles showed specific affiliation with Hela cells other than HEK293 cells, indicating good targeting property of the delivery system. As detected from ex vivo fluorescent imaging, PMA-g-Chol/PEG-FA nanoparticles could accumulate at tumor site with higher selectivity compared to PMA-g-Chol/PEG nanoparticles and DOX x HCl. In vivo antitumor studies confirmed the significant tumor inhibition efficacy of drug-loaded PMA-g-Chol/PEG-FA nanoparticles with lower toxicity to normal tissues than DOX x HCI at the same dosage. PMID:26485931

  7. Chronic graft-versus-host disease in the rat radiation chimera. III. Immunology and immunopathology in rapidly induced models

    SciTech Connect

    Beschorner, W.E.; Tutschka, P.J.; Santos, G.W.

    1983-03-01

    Although chronic graft-versus-host disease (GVHD) frequently develops in the long-term rat radiation chimera, we present three additional models in which a histologically similar disease is rapidly induced. These include adoptive transfer of spleen and bone marrow from rats with spontaneous chronic GVHD into lethally irradiated rats of the primary host strain; sublethal irradiation of stable chimeras followed by a booster transplant; and transfer of spleen cells of chimeras recovering from acute GVHD into second-party (primary recipient strain) or third-party hosts. Some immunopathologic and immune abnormalities associated with spontaneous chronic GVHD were not observed in one or more of the induced models. Thus, IgM deposition in the skin, antinuclear antibodies, and vasculitis appear to be paraphenomena. On the other hand, lymphoid hypocellularity of the thymic medulla, immaturity of splenic follicles, and nonspecific suppressor cells were consistently present in the long term chimeras, and in all models. These abnormalities therefore may be pathogenetically important, or closely related to the development of chronic GVHD.

  8. Bone graft

    MedlinePlus

    A bone graft is surgery to place new bone or bone substitutes into spaces around a broken bone or bone ... A bone graft can be taken from the patient's own healthy bone (this is called an autograft). Or, it can ...

  9. Synthesis and characterization of photoluminescent hybrids of poly( ɛ-caprolactone)-grafted-polyhedral oligosilsesquioxane by using a combination of ring-opening polymerization and click chemistry

    NASA Astrophysics Data System (ADS)

    Cao, Xuan Thang; Showkat, Ali Md; Bach, Long Giang; Jeong, Yeon Tae; Kim, Jong Soo; Lim, Kwon Taek; Gal, Yeong-Soon

    2015-01-01

    Photoluminescent hybrids of poly( ɛ-caprolactone) (PCL), polyhedral oligosilsesquioxane (POSS) and terbium ions (Tb3+) were synthesized by using a combination of ring-opening polymerization (ROP), click chemistry and coordination chemistry. Initially, acetylene functionalized PCL (alkyne-PCL-COOH) was prepared by using ROP of ɛ-caprolactone with propargyl alcohol, and azide-substituted POSS (POSS-N3) was prepared by using the reaction of chloropropyl-heptaisobutyl-substituted POSS with NaN3. The click reaction between alkyne-PCL-COOH and POSS-N3 afforded POSS-g-PCL, which was subsequently coordinated with Tb3+ ions in the presence of 1,10-phenanthroline to produce POSS-g-PCL-Tb3+-Phen. The structures and compositions of the hybrids were investigated by using 1H nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron microscope (FE-SEM), Transmission electron microscopy (TEM), and Thermogravimetric analysis (TGA). The optical properties of POSS-g-PCL-Tb3+-Phen complexes were characterized by using photoluminescence spectroscopy, which showed four high emission bands centered at 489, 545, 584, and 620 nm with excitation at 330 nm. The emission spectra of the europium-ion-coordinated hybrids, POSS-g-PCL-Eu3+-Phen, had four high-intensity peaks, 594, 617, 652 and 686 nm, for an excitation wavelength of 352 nm.

  10. Skin Graft

    PubMed Central

    Shimizu, Ruka; Kishi, Kazuo

    2012-01-01

    Skin graft is one of the most indispensable techniques in plastic surgery and dermatology. Skin grafts are used in a variety of clinical situations, such as traumatic wounds, defects after oncologic resection, burn reconstruction, scar contracture release, congenital skin deficiencies, hair restoration, vitiligo, and nipple-areola reconstruction. Skin grafts are generally avoided in the management of more complex wounds. Conditions with deep spaces and exposed bones normally require the use of skin flaps or muscle flaps. In the present review, we describe how to perform skin grafting successfully, and some variation of skin grafting. PMID:22570780

  11. Thermal analysis evaluation of mechanical properties changes promoted by gamma radiation on surgical polymeric textiles

    NASA Astrophysics Data System (ADS)

    Ferreira, L. M.; Casimiro, M. H.; Oliveira, C.; Cabeço Silva, M. E.; Marques Abreu, M. J.; Coelho, A.

    2002-05-01

    The large number of surgical operations with post-operative infection problems and the appearing of new infectious diseases, contribute to the development of new materials in order to answer the needs of health care services. This development must take into account the modifications promoted by sterilisation methods in materials, namely by gamma radiation. The differential scanning calorimetry (DSC) and thermogravimetry (TGA) techniques show that a nonwoven and a laminate textiles maintain a good molecular cohesion, do not showing high levels of degradation, for gamma radiation dose values lower than 100 kGy in nonwoven and 200 kGy in laminate materials. The tensile strength and the elongation decrease slowly for the nonwoven textile and decrease faster for the laminate textile for 25 and 80 kGy absorbed dose. This paper shows that the DSC and TGA techniques can be helpful for the prevision of mechanical changes occurred in the materials as a consequence of the gamma irradiation.

  12. Plant grafting.

    PubMed

    Melnyk, Charles W; Meyerowitz, Elliot M

    2015-03-01

    Since ancient times, people have cut and joined together plants of different varieties or species so they would grow as a single plant - a process known as grafting (Figures 1 and 2). References to grafting appear in the Bible, ancient Greek and ancient Chinese texts, indicating that grafting was practised in Europe, the Middle East and Asia by at least the 5(th) century BCE. It is unknown where or how grafting was first discovered, but it is likely that natural grafting, the process by which two plants touch and fuse limbs or roots in the absence of human interference (Figure 3), influenced people's thinking. Such natural grafts are generally uncommon, but are seen in certain species, including English ivy. Parasitic plants, such as mistletoe, that grow and feed on often unrelated species may have also contributed to the development of grafting as a technique, as people would have observed mistletoe growing on trees such as apples or poplars. PMID:25734263

  13. Prevention of graft rejection in allogeneic bone marrow transplantation. II. Preclinical studies with three radiation protocols

    SciTech Connect

    Malilay, G.P.; Sevenich, E.A.; Filipovich, A.H. )

    1990-09-01

    Three radiotherapeutic regimens were compared in vitro to determine their immunosuppressive potential against non-MHC-restricted cytotoxic cells. Assays of natural killer and lymphokine-activated killer function, and cytotoxicity against allogeneic cells were used to quantitate the cytotoxic potential of peripheral blood mononuclear cells from healthy individuals following irradiation with a single dose of 1000 cGy on day 0, 1320 cGy of fractionated radiation (165 cGy b.i.d. x 4 days), or split-dose irradiation consisting of 1000 cGy on day 0 followed 5 or 7 days later by 500 cGy. Both irradiated and nonirradiated (control) PBMC cultures were maintained in culture with medium containing interleukin-2, immunophenotyped, and assayed for cytotoxicity from 1 to 8 days after irradiation. Single dose and fractionated-dose irradiation resulted in a progressive decline in cytotoxic capacity, with an 80% inhibition of both NK and LAK cell activity 8 days after onset of irradiation. The split dose of 500 cGy administered 7 days after a dose of 1000 cGy was found to be the most effective in eliminating NK (93% inhibition) and LAK (100% inhibition) cytotoxicity. These data indicate that split-dose irradiation may result in greater immunosuppression than single-dose or fractionated irradiation.

  14. Temperature-responsiveness and biocompatibility of DEGMA/OEGMA radiation-grafted onto PP and LDPE films

    NASA Astrophysics Data System (ADS)

    Ramírez-Jiménez, Alejandro; Alvarez-Lorenzo, Carmen; Concheiro, Angel; Bucio, Emilio

    2014-06-01

    Polypropylene (PP) and low density polyethylene (LDPE) were modified by γ-ray grafting of di(ethylene glycol) methyl ether methacrylate (DEGMA) and oligo (ethylene glycol) methyl ether methacrylate (OEGMA300 or OEGMA475 with Mn 300 and 475 respectively) with different monomer concentrations and mol ratios. The grafting percentage was evaluated as a function of the solvent, irradiation dose, reaction time, temperature, and monomers concentration. The grafted materials were more hydrophilic than the pristine polymers, as observed by contact angle and swelling in water. Temperature-responsive behavior was evaluated using DSC showing transitions between 34 and 48 °C. In vitro hemocompatibility, protein adsorption, cytotoxicity and bacteria adhesion tests were also carried out. Overall, the DEGMA/OEGMA grafting provides hemo and cytocompatible materials that exhibit temperature-responsive hydrophilic features and decreased protein adsorption.

  15. Fixation of three-dimensional states of deformation in polymers by ionizing radiation. Search for new polymeric materials.

    NASA Astrophysics Data System (ADS)

    Schaudy, R.; Wendrinsky, J.; Beer, R. J.; Eberhardsteiner, J.

    1995-02-01

    The fixation of three-dimensional states of deformation in polymers allows the analysis of "special states" of elastic stresses even in the interior of complex constructional units and machine parts. This is the reason for the fact that in spite of the development of modern experimental methods of the analysis of deformation, which are in general restricted to the deformation of the surface of the bodies, the classical "photoelasticity" is still an adequate procedure for solving technical problems. However there are several restrictions on the applicability of the presently used procedures. A potential way to overcome these restrictions is the use of ionizing radiation, which in several polymeric materials causes a more or less perfect fixation of three-dimensional states of deformation. The search for suitable polymers includes the modification of well-known materials like epoxy resins as well as the application and development of materials not yet used in this field of engineering. Preliminary results of the search for such new materials are presented. In selected polymers the stress-optical constant f σ (S) typically increases with dose, whereas the optical creep behaves ambiguous on irradiation.

  16. The effect of nanocomposite polymeric layer on the radiation of antisymmetric zero-order Lamb wave in a piezoelectric plate contacting with liquid

    NASA Astrophysics Data System (ADS)

    Kuznetsova, I. E.; Zaitsev, B. D.; Borodina, I. A.; Shikhabudinov, A. M.; Teplykh, A. A.; Manga, E.; Feuillard, G.

    2013-06-01

    A nanocomposite polymeric layer is proposed to be used for increasing the efficiency of ultrasound radiation into the liquid by antisymmetric zero-order (A0) Lamb waves propagating in piezoelectric plates. The theoretical and experimental investigations of the influence of the nanocomposite polymeric layers on the efficiency and radiation angle of acoustic wave into liquid were carried out. It has been theoretically shown that the use of the layer of the polyethylene of low density with nanoparticles of cadmium sulfide of concentration 25% between the plate of 128YX LiNbO3 and water medium allows to increase the radiation attenuation on ˜1 dB/λ if the ratio of the thicknesses of the layer and plate is equal to 0.16 at the frequency of 1.3 MHz. The experimental data were in a good agreement with theoretical results. It has been also shown that the presence of nanocomposite film leads to the increase of the radiation angle of bulk acoustic wave in liquid and allows the effective operation of the radiator not only in the sweet water but also in salt one. The obtained results may be used for the development of effective radiators/receivers of acoustic waves in liquids for flow meters and for underwater communication systems.

  17. Effects of Electrons, Protons, and Ultraviolet Radiation on Thermophysical Properties of Polymeric Films

    NASA Technical Reports Server (NTRS)

    Russell, Dennis A.; Connell, John W.; Fogdall, Lawrence B.; Winkler, Werner W.

    2001-01-01

    The response of coated thin polymer films to ultraviolet (UV), electron and proton radiation simultaneously has been evaluated, with selected measurements in situ. Exposure was intended to simulate the electron and proton radiation environment near the Earth-Sun Lagrangian points (LI and L2) for five years and approximately 1000 equivalent solar hours (ESH) UV. These orbital environments are relevant to several potential missions such as the Next Generation Space Telescope and Geomagnetic Storm Warning, both of which may use thin film based structures for a sunshade and solar sail, respectively. The thin film candidates (12.5 micrometers thick) consisted of commercially available materials (Kapton(R) E, HN, Upilex(R) S, CP-1, CP-2, TOR-RC, and TOR-LMBP) that were metalized on one side with vapor deposited aluminum. All of the films are aromatic polyimides, with the exception of TORLMBP, which is a copoly(arylene ether benzimidazole). The films were exposed as second surface mirrors and the effects of the exposure on solar absorptance, thermal emittance, and tensile properties were determined. The in situ changes in solar absorptance from Kapton(R) and Upilex(R) were less than 0. 1, whereas the solar absorptance of TOR and CP films increased by more than 0.3 without saturating. The thermal emittance measurements also showed that the Kapton(R) and Upilex(R) materials increased only 1-2%, but the remaining materials increased 5-8%. Based on tensile property measurements made in air following the test, the failure stress of every type of polymer film decreased as a result of irradiation. The polymers most stable in reflectance, namely Upilex(R) and Kapton(R), were also the strongest in tension before irradiation, and they retained the greatest percentage of tensile strength. The films less stable in reflectance were also weaker in tension, and lost more tensile strength as a result of irradiation. The apparent failure strain (as a percent of original gage length) of every type of polymer film except TOR-RC, decreased as a result of irradiation.

  18. Radiation synthesis of multifunctional polymeric hydrogels for oral delivery of insulin.

    PubMed

    Abou Taleb, Manal F

    2013-11-01

    Polyelectrolyte crosslinked hydrogel was synthesized using gamma radiation-induced copolymerization of methacrylic acid (MAA), N,N-dimethyl aminoethyl methacrylate (DMAEMA) in aqueous solution to utilize for oral delivery of insulin. The influence of copolymer composition and pH value of the surrounding medium on the type of water diffusion in the glassy polymer was discussed. In addition, the swelling kinetics tests on MAA/DMAEMA (90/10) reveal that the swelling kinetics of the proposed hydrogel follows a Fickian diffusion process in media of pH 5, and an anomalous diffusion process in media of pH 1.5 and 7.2. The cross-linked three-dimensional polymers were characterized by scanning electron microscopy and FT-IR. In the matrices with increase in the content of MAA had shown increased bioadhesivity. Insulin was entrapped in these gels and the in vitro release profiles were established separately in both (SGF, pH 1.5) and (SIF, pH 7.2). The release profile of insulin showed negligible release in acidic media (SGF, pH 1.5) and sustained release in simulated intestinal fluid (SIF, pH 7.2). Drug release studies showed that the increasing content of MAA in the copolymer enhances release in SIF to design and improve insulin release behavior from these carriers. PMID:24055698

  19. Polymeric microspheres

    DOEpatents

    Walt, David R.; Mandal, Tarun K.; Fleming, Michael S.

    2004-04-13

    The invention features core-shell microsphere compositions, hollow polymeric microspheres, and methods for making the microspheres. The microspheres are characterized as having a polymeric shell with consistent shell thickness.

  20. Structural mechanical properties of radiation-sterilized human Bone-Tendon-Bone grafts preserved by different methods.

    PubMed

    Gut, Grzegorz; Marowska, Joanna; Jastrzebska, Anna; Olender, Ewa; Kamiński, Artur

    2016-06-01

    To avoid the risk of infectious disease transmission from donor to recipient, allografts should be terminally sterilized. In the previous paper (Kaminski et al. in Cell Tissue Bank 10:215-219, 2009) we presented the effect of various methods of preservation (deep fresh freezing, glycerolization, lyophilization), followed by irradiation with different doses of electron beam (EB), on material (intrinsic) mechanical properties of human patellar tendons cut out as for anterior cruciate ligament reconstruction, obtained in failure tensile test. As structural mechanical properties are equally important to predict the behaviour of the graft as a whole functional unit, the purpose of the present paper was to show the results for failure load and elongation, obtained in the same experiment. Paired Bone-Tendon-Bone grafts (BTB) were prepared from cadaveric human patella tendons with both patellar and tibial attachments. They were preserved by deep freezing, glycerolization or lyophilization and subsequently EB-irradiated with the doses of 25, 35, 50 or 100 kGy (fresh-frozen grafts) or a single dose of 35 kGy (glycerolized and lyophilized grafts). Each experimental (irradiated) group was provided with control (non-irradiated), donor-matched group. The specimens from all groups were subjected to mechanical failure tensile test with the use of Instron system in order to measure their structural properties (failure load and elongation). All lyophilized grafts were rehydrated before mechanical testing. In our study we did not observe significant deterioration of structural mechanical properties of BTB grafts processed by fresh-freezing and then terminal sterilized with growing doses of EB up to 100 kGy. In contrast, BTB grafts processed by glycerolization or lyophilization and irradiated with 35 kGy showed significant decrease of failure load. Obtained results suggest that deep-frozen irradiated grafts retain their initial mechanical properties to an extent which does not exclude their clinical application. However, biomechanical investigations constitute only the first step to evaluate the potential clinical usefulness of such allografts and further extensive in vivo studies are needed. PMID:26679928

  1. Physical properties of agave cellulose graft polymethyl methacrylate

    SciTech Connect

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan

    2013-11-27

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm{sup −1} which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.

  2. Photoacid-mediated ring opening polymerization driven by visible light.

    PubMed

    Fu, Changkui; Xu, Jiangtao; Boyer, Cyrille

    2016-06-01

    A novel methodology of visible light regulated ring opening polymerization in the presence of reversible merocyanine-based photoacid was reported for the first time. In combination with a photoinduced radical polymerization technique, a dual wavelength light controlled orthogonal polymerization system was investigated to switch the polymerization between two different monomers and for the preparation of block and graft copolymers in one pot. PMID:27167862

  3. Swelling properties of cassava starch grafted with poly (potassium acrylate-co-acrylamide) superabsorbent hydrogel prepared by ionizing radiation

    NASA Astrophysics Data System (ADS)

    Barleany, Dhena Ria; Ulfiyani, Fida; Istiqomah, Shafina; Heriyanto, Heri; Rahmayetty, Erizal

    2015-12-01

    Natural and synthetic hydrophylic polymers can be phisically or chemically cross-linked in order to produce hydrogels. Starch based hydrogels grafted with copolymers from acrylic acid or acrylamide have become very popular for water absorbent application. Superabsorbent hydrogels made from Cassava starch grafted with poly (potassium acrylate-co-acrylamide) were prepared by using of ϒ-irradiation method. Various important parameters such as irradiation doses, monomer to Cassava starch ratio and acrylamide content were investigated. The addition of 7,5 % w w-1 acrylamide into the reaction mixture generated a starch graft copolymer with a water absorption in distilled water as high as 460 g g-1 of its dried weight. The effectivity of hydrogel as superabsorbent for aqueous solutions of NaCl and urea was evaluated. The obtained hydrogel showed the maximum absorptions of 317 g g-1 and 523 g g-1 for NaCl and urea solution, respectively (relative to its own dry weight). The structure of the graft copolymer was analyzed by using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM).

  4. Role of radiolytically generated species in radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution: Steady state and pulse radiolysis study

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Y. K.; Mohan, H.; Sabharwal, S.; Majali, A. B.

    2000-06-01

    Radiation induced polymerization of sodium p-styrene sulphonate (SSS) in aqueous solution has been investigated by steady state and pulse radiolysis techniques. Effect of dose, dose rate, monomer concentration, pH and ambient conditions on polymerization was investigated. The reactions of primary radicals of water radiolysis such as OH radical, e -aq, H atom, O rad - and some oxidizing radicals like N rad 3, Cl rad -2,Br rad -2, and reducing specie like CO rad -2 with SSS have also been investigated. SSS reacts with OH radical with a rate constant of 5.9×10 9 dm 3 mol -1s -1 at pH 6.3. The results indicate that ˜83% of OH radicals undergo electron transfer reaction resulting in a cation radical species while remaining ˜17% react via addition reaction. The hydrated electron reacts with SSS with a rate constant 1.3×10 10 dm 3 mol -1 s -1 to form an anion that undergoes fast protonation to form H-adduct at pH 6.3. At high pH (>10) the anion is able to transfer electron to methyl vilogen and p-nitro aceto phenone ( p-NAP) where as H-adduct is unable to transfer electron. At pH ˜1 H atom reaction with SSS is diffusion controlled with a rate constant of 5×10 9 dm 3 mol -1 s -1 and results in formation of H adduct. It was seen that anion reacts with solute an order faster than cation generated radiolytically indicating anionic initiation of polymerization of SSS. Molecular weight of the polymer formed by radiation polymerization, determined by viscosity measurement, are of the order of 10 7 and higher molecular weight polymers are obtained at lower dose rates. In presence of a crosslinking agent gelation of polymer is much faster than the monomer and a polymer concentration ˜20% is most efficiently crosslinked.

  5. Uranium Recovery from Seawater: Development of Fiber Adsorbents Prepared via Atom-Transfer Radical Polymerization

    SciTech Connect

    Saito, Tomonori; Brown, Suree; Chatterjee, Sabornie; Kim, Jungseung; Tsouris, Costas; Mayes, Richard T; Kuo, Li-Jung; Gill, Gary; Oyola, Yatsandra; Janke, Christopher James; Dai, Sheng

    2014-01-01

    A novel adsorbent preparation method using atom-transfer radical polymerization (ATRP) combined with radiation-induced graft polymerization (RIGP) was developed to synthesize an adsorbent for uranium recovery from seawater. The ATRP method allowed a much higher degree of grafting on the adsorbent fibers (595 2818%) than that allowed by RIGP alone. The adsorbents were prepared with varied composition of amidoxime groups and hydrophilic acrylate groups. The successful preparation revealed that both ligand density and hydrophilicity were critical for optimal performance of the adsorbents. Adsorbents synthesized in this study showed a relatively high performance (141 179 mg/g at 49 62 % adsorption) in laboratory screening tests using a uranium concentration of ~6 ppm. This performance is much higher than that of known commercial adsorbents. However, actual seawater experiment showed impeded performance compared to the recently reported high-surface-area-fiber adsorbents, due to slow adsorption kinetics. The impeded performance motivated an investigation of the effect of hydrophilic block addition on the graft chain terminus. The addition of hydrophilic block on the graft chain terminus nearly doubled the uranium adsorption capacity in seawater, from 1.56 mg/g to 3.02 mg/g. The investigation revealed the importance of polymer chain conformation, in addition to ligand and hydrophilic group ratio, for advanced adsorbent synthesis for uranium recovery from seawater.

  6. Studies in Fat Grafting: Part III. Fat grafting irradiated tissue: Improved skin quality and decreased fat graft retention

    PubMed Central

    Garza, Rebecca M.; Paik, Kevin J.; Chung, Michael T.; Duscher, Dominik; Gurtner, Geoffrey C.; Longaker, Michael T.; Wan, Derrick C.

    2014-01-01

    Background Following radiation therapy, skin becomes fibrotic and can present a difficult problem for reconstructive surgeons. There is an increasing belief that fat grafting under radiated skin can reverse the damage caused by radiation. The present study evaluated the effect of fat grafting on irradiated skin, along with fat graft quality and retention rates in irradiated tissue. Methods Nine adult Crl:NU-Foxn1nu CD-1 mice received 30 Gy external beam radiation of the scalp. Four weeks following radiation, scalp skin from irradiated and non-irradiated mice was harvested and compared histologically for dermal thickness, collagen content, and vascular density. Human fat grafts were then injected in the subcutaneous plane of the scalp. Skin assessment was performed in the irradiated group at 2 and 8 weeks post-grafting, and fat graft retention was measured at baseline and every 2 weeks up to 8 weeks post-grafting using micro-CT. Finally, fat graft samples were explanted at 8 weeks, and quality scoring was performed. Results Fat grafting resulted in decreased dermal thickness, decreased collagen content, and increased vascular density in irradiated skin. CT analysis revealed significantly decreased fat graft survival in the irradiated group when compared to the non-irradiated group. Histological scoring of explanted fat grafts demonstrated no difference in quality between the irradiated and non-irradiated groups. Conclusions Fat grafting attenuates dermal collagen deposition and vessel depletion characteristic of radiation fibrosis. Although fat graft retention rates are significantly lower in irradiated than non-irradiated tissue, the quality of retained fat between the groups is similar. PMID:25068325

  7. PREFACE: IUMRS-ICA 2008 Symposium, Sessions 'X. Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science' and 'Y. Frontier of Polymeric Nano-Soft-Materials - Precision Polymer Synthesis, Self-assembling and Their Functionalization'

    NASA Astrophysics Data System (ADS)

    Takahara, Atsushi; Kawahara, Seiichi

    2009-09-01

    Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science (Symposium X of IUMRS-ICA2008) Toshiji Kanaya, Kohji Tashiro, Kazuo Sakura Keiji Tanaka, Sono Sasaki, Naoya Torikai, Moonhor Ree, Kookheon Char, Charles C Han, Atsushi Takahara This volume contains peer-reviewed invited and contributed papers that were presented in Symposium X 'Applications of Synchrotron Radiation and Neutron Beam to Soft Matter Science' at the IUMRS International Conference in Asia 2008 (IUMRS-ICA 2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. Structure analyses of soft materials based on synchrotron radiation (SR) and neutron beam have been developed steadily. Small-angle scattering and wide-angle diffraction techniques clarified the higher-order structure as well as time dependence of structure development such as crystallization and microphase-separation. On the other hand, reflectivity, grazing-incidence scattering and diffraction techniques revealed the surface and interface structural features of soft materials. From the viewpoint of strong interests on the development of SR and neutron beam techniques for soft materials, the objective of this symposium is to provide an interdisciplinary forum for the discussion of recent advances in research, development, and applications of SR and neutron beams to soft matter science. In this symposium, 21 oral papers containing 16 invited papers and 14 poster papers from China, India, Korea, Taiwan, and Japan were presented during the three-day symposium. As a result of the review of poster and oral presentations of young scientists by symposium chairs, Dr Kummetha Raghunatha Reddy (Toyota Technological Institute) received the IUMRS-ICA 2008 Young Researcher Award. We are grateful to all invited speakers and many participants for valuable contributions and active discussions. Organizing committee of Symposium (IUMRS-ICA 2008) Professor Toshiji Kanaya (Kyoto University) Professor Kohji Tashiro (Toyota Technological Institute) Professor Kazuo Sakurai(Kitakyushu University) Professor Keiji Tanaka (Kyushu University) Dr Sono Sasaki (JASRI/Spring-8) Professor Naoya Torikai (KENS) Professor Moonhor Ree (POSTECH) Professor Kookheon Char (Seoul National University) Professor Charles C Han (CAS) Professor Atsushi Takahara(Kyushu University) Frontier of Polymeric Nano-Soft-Materials, Precision Polymer Synthesis, Self-assembling and Their Functionalization (Symposium Y of IUMRS-ICA2008) Seiichi Kawahara, Rong-Ming Ho, Hiroshi Jinnai, Masami Kamigaito, Takashi Miyata, Hiroshi Morita, Hideyuki Otsuka, Daewon Sohn, Keiji Tanaka It is our great pleasure and honor to publish peer-reviewed papers, presented in Symposium Y 'Frontier of Polymeric Nano-Soft-Materials Precision Polymer Synthesis, Self-assembling and Their Functionalization' at the International Union of Materials Research Societies International Conference in Asia 2008 (IUMRS-ICA2008), which was held on 9-13 December 2008, at Nagoya Congress Center, Nagoya, Japan. 'Polymeric nano-soft-materials' are novel outcomes based on a recent innovative evolution in polymer science, i.e. precision polymer synthesis, self-assembling and functionalization of multi-component systems. The materials are expected to exhibit specific functions and unique properties due to their hierarchic morphologies brought either by naturally-generated ordering or by artificial manipulation of the systems, e.g., crystallization and phase-separation. The emerging precision synthesis has brought out new types of polymers with well-controlled primary structures. Furthermore, the surface and interface of the material are recognized to play an important role in the outstanding mechanical, electrical and optical properties, which are required for medical and engineering applications. In order to understand structure-property relationships in the nano-soft-materials, it is indispensable to develop novel characterization techniques. Symposium Y aimed to provide recent advances in polymer synthesis, self-assembling processes and morphologies, and functionalization of nano-soft-materials in order to initiate mutual and collaborative research interest that is essential to develop revolutionarily new nano-soft-materials in the decades ahead. Four Keynote lectures, 15 invited talks and 30 posters presented important new discoveries in polymeric nano-soft-materials, precision polymer synthesis, self-assembling and their functionalization. As for the precision polymer synthesis, the latest results were provided for studies on synthesis of polyrotaxane with movable graft chains, organic-inorganic hybridization of polymers, supra-molecular coordination assembly of conjugated polymers, precision polymerization of adamantane-containing monomers, production of high density polymer brush and synthesis of rod coil type polymer. The state-of-the-art results were introduced for the formation of nano-helical-structure of block copolymer containing asymmetric carbon atoms, self-assembling of block copolymers under the electric field, self-assembling of liquid crystalline elastomers, preparation of nano cylinder template films and mesoscopic simulation of phase transition of polymers and so forth. Moreover, recent advantages of three-dimensional electron microtomography and scanning force microscopy were proposed for analyses of nano-structures and properties of polymeric multi-component systems. Syntheses, properties and functions of slide-ring-gel, organic-inorganic hybrid hydrogels, hydrogel nano-particles, liquid-crystalline gels, the self-oscillating gels, and double network gels attracted participants' attention. Modifications of naturally occurring polymeric materials with supercritical carbon dioxide were introduced as a novel technology. Some of the attractive topics are presented in this issue. We are grateful to all the speakers and participants for valuable contributions and active discussions. Organizing committee of Symposium Y (IUMRS-ICA 2008) Chair Seiichi Kawahara (Nagaoka University of Technology, Japan) Vice Chairs Rong-Ming Ho (National Tsing Hua University, Taiwan) Hiroshi Jinnai (Kyoto Institute of Technology, Japan) Masami Kamigaito (Nagoya University, Japan) Takashi Miyata (Kansai University, Japan) Hiroshi Morita (National Institute of Advanced Industrial Science and Technology, Japan) Hideyuki Otsuka (Kyushu University, Japan) Daewon Sohn (Hanyang University, Korea) Keiji Tanaka (Kyushu University, Japan)

  8. Surface treatment of biomaterials by gamma and swift heavy ions grafting

    NASA Astrophysics Data System (ADS)

    Porté-Durrieu, M. C.; Aymes-Chodur, C.; Vergne, C.; Betz, N.; Baquey, Ch.

    1999-05-01

    To date, the successful substitution of small diameter arteries by vascular grafts has not been achieved in humans. In order to reduce their thrombogenicity which remains the major obstacle, polymeric materials endowed with a specific affinity for Antithrombin III (ATIII) and thus able to catalyse the inhibition of thrombin by ATIII, as heparin does, were devised. Sulfonate and sulfonamide groups were introduced on phenyl rings belonging to styrene residues which were radiation grafted (swift heavy ions and gamma radiation) onto poly(vinylene difluoride) (PVDF) and poly(hexafluoropropylene vinylidene fluoride) (P(VDF-HFP)). Contrary to gamma radiation grafting, with swift heavy ions grafting, only small regions are modified; thus, the properties of the initial substrate are preserved. A characterization of surface topography was carried out by Scanning Electron Microscopy and Atomic Force Microscopy. The efficacy of the surface modification was monitored with respect to the total amount of bound "heparin-like" molecules measured by a toluidine blue assay, and the anticoagulant potential estimated by the thrombin time test.

  9. Effect of bidispersity in grafted chain length on grafted chain conformations and potential of mean force between polymer grafted nanoparticles in a homopolymer matrix.

    PubMed

    Nair, Nitish; Wentzel, Nathaniel; Jayaraman, Arthi

    2011-05-21

    In efforts to produce polymeric materials with tailored physical properties, significant interest has grown around the ability to control the spatial organization of nanoparticles in polymer nanocomposites. One way to achieve controlled particle arrangement is by grafting the nanoparticle surface with polymers that are compatible with the matrix, thus manipulating the interfacial interactions between the nanoparticles and the polymer matrix. Previous work has shown that the molecular weight of the grafted polymer, both at high grafting density and low grafting density, plays a key role in dictating the effective inter-particle interactions in a polymer matrix. At high grafting density nanoparticles disperse (aggregate) if the graft molecular weight is higher (lower) than the matrix molecular weight. At low grafting density the longer grafts can better shield the nanoparticle surface from direct particle-particle contacts than the shorter grafts and lead to the dispersion of the grafted particles in the matrix. Despite the importance of graft molecular weight, and evidence of non-trivial effects of polydispersity of chains grafted on flat surfaces, most theoretical work on polymer grafted nanoparticles has only focused on monodisperse grafted chains. In this paper, we focus on how bidispersity in grafted chain lengths affects the grafted chain conformations and inter-particle interactions in an implicit solvent and in a dense homopolymer polymer matrix. We first present the effects of bidispersity on grafted chain conformations in a single polymer grafted particle using purely Monte Carlo (MC) simulations. This is followed by calculations of the potential of mean force (PMF) between two grafted particles in a polymer matrix using a self-consistent Polymer Reference Interaction Site Model theory-Monte Carlo simulation approach. Monte Carlo simulations of a single polymer grafted particle in an implicit solvent show that in the bidisperse polymer grafted particles with an equal number of short and long grafts at low to medium grafting density, the short grafts are in a more coiled up conformation (lower radius of gyration) than their monodisperse counterparts to provide a larger free volume to the longer grafts so they can gain conformational entropy. The longer grafts do not show much difference in conformation from their monodisperse counterparts at low grafting density, but at medium grafting density the longer grafts exhibit less stretched conformations (lower radius of gyration) as compared to their monodisperse counterparts. In the presence of an explicit homopolymer matrix, the longer grafts are more compressed by the matrix homopolymer chains than the short grafts. We observe that the potential of mean force between bidisperse grafted particles has features of the PMF of monodisperse grafted particles with short grafts and monodisperse grafted particles with long grafts. The value of the PMF at contact is governed by the short grafts and values at large inter-particle distances are governed by the longer grafts. Further comparison of the PMF for bidisperse and monodisperse polymer grafted particles in a homopolymer matrix at varying parameters shows that the effects of matrix chain length, matrix packing fraction, grafting density, and particle curvature on the PMF between bidisperse polymer grafted particles are similar to those seen between monodisperse polymer grafted particles. PMID:21599087

  10. Impact of reaction conditions on grafting acrylamide onto starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have explored the radical initiated graft polymerization reaction of acrylamide onto starch where the solvent, concentration, temperature and reaction times were varied. We have found that the morphology of the resulting grafted polymer is dramatically different and is dependent on the reaction c...

  11. Polymeric surfactants in disperse systems.

    PubMed

    Tadros, Tharwat

    2009-01-01

    This overview starts with a section on general classification of polymeric surfactants. Both homopolymers, block and graft copolymers are described. The solution properties of polymeric surfactants is described by using the Flory-Huggins theory. Particular attention is given to the effect of solvency of the medium for the polymer chains. The adsorption and conformation of homopolymers, block and graft copolymers at the solid/liquid interface is described. The theories of polymer adsorption and their predictions are briefly described. This is followed by a description of the experimental techniques that can be applied to study polymeric surfactant adsorption. Examples of adsorption isotherms of non-ionic polymeric surfactants are given. The effect of solvency on the adsorption amount is also described. Results for the adsorbed layer thickness of polymeric surfactants are given with particular attention to the effect of molecular weight. The interaction between particles containing adsorbed layers is described in terms of the unfavorable mixing of the stabilizing chains when these are in good solvent conditions. The entropic, volume restriction or elastic interaction that occurs on considerable overlap is also described. Combination of these two effects forms the basis of the theory of steric stabilization. The energy-distance curve produced with these sterically stabilized systems is described with particular attention of the effect of the ratio of adsorbed layer thickness to droplet radius. Examples of oil-in-water (O/W) and water-in-oil (W/O) emulsions stabilized with polymeric surfactants are given. Of particular interest is the O/W emulsions stabilized using hydrophobically modified inulin (INUTEC((R))SP1). The emulsions produced are highly stable against coalescence both in water and high electrolyte concentrations. This is accounted for by the multipoint attachment of the polymeric surfactant to the oil droplets with several alkyl groups and the strongly hydrated loops and tails of linear polyfructose. Evidence of this high stability was obtained from disjoining pressure measurements. Stabilization of suspensions using INUTEC((R))SP1 was described with particular reference to latexes that were prepared using emulsion polymerization. The high stability of the latexes is attributed to the strong adsorption of the polymeric surfactant on the particle surfaces and the enhanced steric stabilization produced by the strongly hydrated polyfructose loops and tails. Evidence for such high stability was obtained using Atomic Force Microscopy (AFM) measurements. The last part of the overview described the preparation and stabilization of nano-emulsions using INUTEC((R))SP1. In particular the polymeric surfactant was very effective in reducing Ostwald ripening as a result of its strong adsorption and the Gibbs elasticity produced by the polymeric surfactant. PMID:19041086

  12. Structure-function properties of starch spherulites grafted with poly(methyl acrylate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Spherulites, produced by steam jet-cooking high-amylose starch and oleic acid, were grafted with methyl acrylate, both before and after removal of un-complexed amylopectin. For comparison, granular high-amylose corn starch was graft polymerized in a similar manner. The amount of grafted and ungrafte...

  13. Structure-function properties of starch graft poly(methyl acrylate)copolymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Spherulites, produced by steam jet-cooking high-amylose starch and oleic acid, were grafted with methyl acrylate, both before and after removal of un-complexed amylopectin. For comparison, granular high-amylose corn starch was graft polymerized in a similar manner. The amount of grafted and ungrafte...

  14. Synthesis and characterization of superabsorbent polymer prepared by radiation-induced graft copolymerization of acrylamide onto carboxymethyl cellulose for controlled release of agrochemicals

    NASA Astrophysics Data System (ADS)

    Hemvichian, Kasinee; Chanthawong, Auraruk; Suwanmala, Phiriyatorn

    2014-10-01

    Superabsorbent polymer (SAP) was synthesized by radiation-induced grafting of acrylamide (AM) onto carboxymethyl cellulose (CMC) in the presence of a crosslinking agent, N,N‧-methylenebisacrylamide (MBA). The effects of various parameters, such as dose, the amount of CMC, AM, MBA and ionic strength on the swelling ratio were investigated. In order to evaluate its controlled release potential, SAP was loaded with potassium nitrate (KNO3) as an agrochemical model and its potential for controlled release of KNO3 was studied. The amount of released KNO3 was analyzed by an inductively coupled plasma mass spectrometry (ICP-MS). The results from controlled release experiment agreed very well with the results from swelling experiment. The synthesized SAP was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The obtained SAP exhibited a swelling ratio of 190 g/g of dry gel.

  15. Production of monodisperse, polymeric microspheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Rhim, Won-Kyu (Inventor); Hyson, Michael T. (Inventor); Chang, Manchium (Inventor)

    1990-01-01

    Very small, individual polymeric microspheres with very precise size and a wide variation in monomer type and properties are produced by deploying a precisely formed liquid monomer droplet, suitably an acrylic compound such as hydroxyethyl methacrylate into a containerless environment. The droplet which assumes a spheroid shape is subjected to polymerizing radiation such as ultraviolet or gamma radiation as it travels through the environment. Polymeric microspheres having precise diameters varying no more than plus or minus 5 percent from an average size are recovered. Many types of fillers including magnetic fillers may be dispersed in the liquid droplet.

  16. Radiation and photografting as complementary techniques for immobilizing bioactive materials

    NASA Astrophysics Data System (ADS)

    Garnett, J. L.; Jankiewicz, S. V.; Long, M. A.; Sangster, D. F.

    The technique of radiation grafting to immobilize a typical enzyme, trypsin, to three representative backbone polymers namely polypropylene, PVC and polystyrene, is described. The process involves the simultaneous grafting of p-nitrostyrene to the polymer, the nitro group subsequently being converted to its isothiocyanato derivative to which trypsin is attached. For this immobilization work, the utilization of additives which enhance grafting is shown to be an advantage. Typical of the additives used are mineral acids (?0.1M) and polyfunctional monomers (?1% v/v), the two acting in a synergistic fashion when used together. A new class of additives, namely metal salts such as LiClO 4, which also increase grafting yields has now been discovered. The reactivity of these salts in grafting enhancement is compared with that of mineral acid. A new model for the modus operandi of metal salts as well as acids in grafting enhancement is proposed whereby increased grafting yields are attributed to increased partitioning of monomer into the graft region in the presence of ionic solutes. The significance of using these additives to prepare radiation copolymers for enzyme immobilization is discussed. In addition to ionizing radiation, UV is also shown to be of value as an initiator for the preparation of graft copolymers for enzyme immobilization, however the presence of sensitizer in the copolymer may limit the photografting method. The possibility of using radiation curing processes involving electron beam (EB) and high powered (300 W/inch) UV sources for immobilization work has been explored and found to be feasible. The curing system possesses great potential for the current immobilization work since complete polymerization is achieved in a fraction of a second.

  17. Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization from Chlorinated Polypropylene and Polyethylene Trunk Fibers

    SciTech Connect

    Brown, Suree; Chatterjee, Sabornie; Li, Meijun; Yue, Yanfeng; Tsouris, Costas; Janke, Christopher J.; Saito, Tomonori; Dai, Sheng

    2015-12-10

    Seawater contains a large amount of uranium (~4.5 billion tons) which can serve as a limitless supply of an energy source. However, in order to make the recovery of uranium from seawater economically feasible, lower manufacturing and deployment costs are required, and thus, solid adsorbents must have high uranium uptake, reusability, and high selectivity toward uranium. In this study, atom-transfer radical polymerization (ATRP), without the radiation-induced graft polymerization (RIGP), was used for grafting acrylonitrile (AN) and tert-butyl acrylate (tBA) from a new class of trunk fibers, forming adsorbents in a readily deployable form. The new class of trunk fibers was prepared by the chlorination of PP round fiber, hollow-gear-shaped PP fiber, and hollow-gear-shaped PE fiber. During ATRP, degrees of grafting (d.g.) varied according to the structure of active chlorine sites on trunk fibers and ATRP conditions, and the d.g. as high as 2570% was obtained. Resulting adsorbent fibers were evaluated in U-spiked simulated seawater and the maximum adsorption capacity of 146.6 g U/kg, much higher than that of a standard adsorbent JAEA fiber (75.1 g/kg), was obtained. This new type of trunk fibers can be used for grafting a variety of uranium-interacting ligands, including designed ligands that are highly selective toward uranium.

  18. Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization from Chlorinated Polypropylene and Polyethylene Trunk Fibers

    DOE PAGESBeta

    Brown, Suree; Chatterjee, Sabornie; Li, Meijun; Yue, Yanfeng; Tsouris, Costas; Janke, Christopher J.; Saito, Tomonori; Dai, Sheng

    2015-12-10

    Seawater contains a large amount of uranium (~4.5 billion tons) which can serve as a limitless supply of an energy source. However, in order to make the recovery of uranium from seawater economically feasible, lower manufacturing and deployment costs are required, and thus, solid adsorbents must have high uranium uptake, reusability, and high selectivity toward uranium. In this study, atom-transfer radical polymerization (ATRP), without the radiation-induced graft polymerization (RIGP), was used for grafting acrylonitrile (AN) and tert-butyl acrylate (tBA) from a new class of trunk fibers, forming adsorbents in a readily deployable form. The new class of trunk fibers wasmore » prepared by the chlorination of PP round fiber, hollow-gear-shaped PP fiber, and hollow-gear-shaped PE fiber. During ATRP, degrees of grafting (d.g.) varied according to the structure of active chlorine sites on trunk fibers and ATRP conditions, and the d.g. as high as 2570% was obtained. Resulting adsorbent fibers were evaluated in U-spiked simulated seawater and the maximum adsorption capacity of 146.6 g U/kg, much higher than that of a standard adsorbent JAEA fiber (75.1 g/kg), was obtained. This new type of trunk fibers can be used for grafting a variety of uranium-interacting ligands, including designed ligands that are highly selective toward uranium.« less

  19. Laundering durable antibacterial cotton fabrics grafted with pomegranate-shaped polymer wrapped in silver nanoparticle aggregations

    NASA Astrophysics Data System (ADS)

    Liu, Hanzhou; Lv, Ming; Deng, Bo; Li, Jingye; Yu, Ming; Huang, Qing; Fan, Chunhai

    2014-08-01

    To improve the laundering durability of the silver functionalized antibacterial cotton fabrics, a radiation-induced coincident reduction and graft polymerization is reported herein where a pomegranate-shaped silver nanoparticle aggregations up to 500 nm can be formed due to the coordination forces between amino group and silver and the wrapping procedure originated from the coincident growth of the silver nanoparticles and polymer graft chains. This pomegranate-shaped silver NPAs functionalized cotton fabric exhibits outstanding antibacterial activities and also excellent laundering durability, where it can inactivate higher than 90% of both E. coli and S. aureus even after 50 accelerated laundering cycles, which is equivalent to 250 commercial or domestic laundering cycles.

  20. Laundering durable antibacterial cotton fabrics grafted with pomegranate-shaped polymer wrapped in silver nanoparticle aggregations

    PubMed Central

    Liu, Hanzhou; Lv, Ming; Deng, Bo; Li, Jingye; Yu, Ming; Huang, Qing; Fan, Chunhai

    2014-01-01

    To improve the laundering durability of the silver functionalized antibacterial cotton fabrics, a radiation-induced coincident reduction and graft polymerization is reported herein where a pomegranate-shaped silver nanoparticle aggregations up to 500 nm can be formed due to the coordination forces between amino group and silver and the wrapping procedure originated from the coincident growth of the silver nanoparticles and polymer graft chains. This pomegranate-shaped silver NPAs functionalized cotton fabric exhibits outstanding antibacterial activities and also excellent laundering durability, where it can inactivate higher than 90% of both E. coli and S. aureus even after 50 accelerated laundering cycles, which is equivalent to 250 commercial or domestic laundering cycles. PMID:25082297

  1. Laundering durable antibacterial cotton fabrics grafted with pomegranate-shaped polymer wrapped in silver nanoparticle aggregations.

    PubMed

    Liu, Hanzhou; Lv, Ming; Deng, Bo; Li, Jingye; Yu, Ming; Huang, Qing; Fan, Chunhai

    2014-01-01

    To improve the laundering durability of the silver functionalized antibacterial cotton fabrics, a radiation-induced coincident reduction and graft polymerization is reported herein where a pomegranate-shaped silver nanoparticle aggregations up to 500 nm can be formed due to the coordination forces between amino group and silver and the wrapping procedure originated from the coincident growth of the silver nanoparticles and polymer graft chains. This pomegranate-shaped silver NPAs functionalized cotton fabric exhibits outstanding antibacterial activities and also excellent laundering durability, where it can inactivate higher than 90% of both E. coli and S. aureus even after 50 accelerated laundering cycles, which is equivalent to 250 commercial or domestic laundering cycles. PMID:25082297

  2. Low Radiation Dose and Low Cell Dose Increase the Risk of Graft Rejection in a Canine Hematopoietic Stem Cell Transplantation Model.

    PubMed

    Lange, Sandra; Steder, Anne; Glass, Änne; Killian, Doreen; Wittmann, Susanne; Machka, Christoph; Werner, Juliane; Schäfer, Stephanie; Roolf, Catrin; Junghanss, Christian

    2016-04-01

    The canine hematopoietic stem cell transplantation (HSCT) model has become accepted in recent decades as a good preclinical model for the development of new transplantation strategies. Information on factors associated with outcome after allogeneic HSCT are a prerequisite for designing new risk-adapted transplantation protocols. Here we report a retrospective analysis aimed at identifying risk factors for allograft rejection in the canine HSCT model. A total of 75 dog leukocyte antigen-identical sibling HSCTs were performed since 2003 on 10 different protocols. Conditioning consisted of total body irradiation at 1.0 Gy (n = 20), 2.0 Gy (n = 40), or 4.5 Gy (n = 15). Bone marrow was infused either intravenously (n = 54) or intraosseously (n = 21). Cyclosporin A alone or different combinations of cyclosporine A, mycophenolate mofetil, and everolimus were used for immunosuppression. A median cell dose of 3.5 (range, 1.0 to 11.8) total nucleated cells (TNCs)/kg was infused. Cox analyses were used to assess the influence of age, weight, radiation dose, donor/recipient sex, type of immunosuppression, and cell dose (TNCs, CD34(+) cells) on allograft rejection. Initial engraftment occurred in all dogs. Forty-two dogs (56%) experienced graft rejection at median of 11 weeks (range, 6 to 56 weeks) after HSCT. Univariate analyses revealed radiation dose, type of immunosuppression, TNC dose, recipient weight, and recipient age as factors influencing long-term engraftment. In multivariate analysis, low radiation dose (P < .001) and low TNC cell count (P = .044) were identified as significant independent risk factors for graft rejection. Peripheral blood mononuclear cell chimerism ≥30% (P = .008) and granulocyte chimerism ≥70% (P = .023) at 4 weeks after HSCT were independent predictors of stable engraftment. In summary, these data indicate that even in low-dose total body irradiation-based regimens, the irradiation dose is important for engraftment. The level of blood chimerism at 4 weeks post-HSCT was predictive of long-term engraftment in the canine HSCT model. PMID:26802322

  3. Polymeric nanoparticles

    PubMed Central

    Bolhassani, Azam; Javanzad, Shabnam; Saleh, Tayebeh; Hashemi, Mehrdad; Aghasadeghi, Mohammad Reza; Sadat, Seyed Mehdi

    2014-01-01

    Nanocarriers with various compositions and biological properties have been extensively applied for in vitro/in vivo drug and gene delivery. The family of nanocarriers includes polymeric nanoparticles, lipid-based carriers (liposomes/micelles), dendrimers, carbon nanotubes, and gold nanoparticles (nanoshells/nanocages). Among different delivery systems, polymeric carriers have several properties such as: easy to synthesize, inexpensive, biocompatible, biodegradable, non-immunogenic, non-toxic, and water soluble. In addition, cationic polymers seem to produce more stable complexes led to a more protection during cellular trafficking than cationic lipids. Nanoparticles often show significant adjuvant effects in vaccine delivery since they may be easily taken up by antigen presenting cells (APCs). Natural polymers such as polysaccharides and synthetic polymers have demonstrated great potential to form vaccine nanoparticles. The development of new adjuvants or delivery systems for DNA and protein immunization is an expanding research field. This review describes polymeric carriers especially PLGA, chitosan, and PEI as vaccine delivery systems. PMID:24128651

  4. Viability of porcine nasal septal cartilage grafts following Nd:YAG (n=1.32μm) laser radiation

    NASA Astrophysics Data System (ADS)

    Chao, Kenneth K. H.; Wong, Brian J.; Kim, Hong K.; Milner, Thomas E.; Sung, Chung-Ho; Sobol, Emil N.; Nelson, J. Stuart

    2000-06-01

    Mechanically deformed morphologic cartilage grafts undergo a temperature dependent phase transformation during sustained laser irradiation that results in reshaping of the specimen. While thermal, optical, and mechanical properties of cartilage undergoing laser heating have been previously investigated, the viability of these irradiated grafts has yet to be examined closely until now. In this study, chondrocyte viability following laser irradiation was determined by measuring the incorporation of radiolabelled sulfate (Na 35SO4-2) into proteoglycan (PTG) macromolecules. Proteoglycans are highly sulfated and are the principal molecular constituents of cartilage matrix. Their synthesis directly reflects chondrocyte viability. By measuring the scintillation counts of 35SO4-2 uptake and normalizing the value by the total protein content of each specimen we can determine the level of PTG synthesis rates following laser reshaping. Regional baseline PTG synthesis rates as a function of location was determined by dividing each specimen into six regions. All regions except the most cephalic are demonstrated similar PTG synthesis rates. The most cephalic region exhibited a significantly greater PTG synthesis rates. In order to establish a positive control for this study, specimens were immersed in boiling saline water for approximately 40 minutes. The boiled specimens demonstrated a fivefold increase in normalized radioisotope uptake and suggest that the non-specific uptake of radioactive Na35SO4-2 is caused by structural alterations in the collagen matrix caused by extensive thermal exposure. To avoid this thermal artifact, another positive control was established using nitric oxide was to induce apoptosis of the chondrocytes, resulting in significantly lower PTG synthesis compared to untreated tissue. Cartilage specimens (25 X 10 X 2 mm) were irradiated with light emitted from an Nd:YAG laser (25 W/cm2, (lambda) equals 1.32 micrometer) while radiometric surface temperature, internal stress, and backscattered light were simultaneously recorded. Individual specimens underwent either one, two, or three sequential laser exposures with the duration of each exposure determined in real-time from observation of characteristic changes in integrated backscattered light intensity that correlate with thermal mediated stress relaxation. A five-minute time interval between each irradiation was given to allow the cartilage to return to thermal equilibrium. Average laser exposure for each irradiation sequence was recorded (5, 8.3, 12.2 sec). PTG synthesis decreased with increasing laser exposure, but was noted to remain above baseline levels for NO treated tissue. To further refine these results and minimize the effect of regional tissue variations, 7 mm diameter discs excised from the most cephalic portions and a middle region of the pig nasal septal cartilages were irradiated. A reduction of PTG synthesis rates was noted with each successive irradiation, suggesting that laser mediated cartilage reshaping acutely does not eliminate the population of viable chondrocytes. The degree of reduction in PTG synthesis is dependent upon the time-temperature dependent heating profile created during laser irradiation, and carefully monitored dosimetry is necessary to ensure chondrocyte viability.

  5. Effects of high energy simulated space radiation on polymeric second-surface mirrors. [thermal control coatings - performance tests

    NASA Technical Reports Server (NTRS)

    Eogdall, L. B.; Cannaday, S. S.

    1975-01-01

    A radiation effects experimental program was performed, in which second surface mirror type thermal control coatings were exposed to ultraviolet radiation, electrons, and protons simultaneously. Stability was assessed by making periodic spectral reflectance measurements in situ (and in air after testing for comparison). Solar absorption coefficients were derived by computer. Many of the exposed materials showed large amounts of degradation in reflectance absorptance, principally due to the electron exposure. A series of tests was conducted, leading to the identification of a modified second surface mirror that shows considerable improvement and promise for stability during thermal control applications in a charged particle space radiation environment.

  6. Location and size of nanoscale free-volume holes in crosslinked- polytetrafluoroethylene-based graft-type polymer electrolyte membranes determined by positron annihilation lifetime spectroscopy

    NASA Astrophysics Data System (ADS)

    Sawada, Shin-ichi; Yabuuchi, Atsushi; Maekawa, Masaki; Kawasuso, Atsuo; Maekawa, Yasunari

    2013-06-01

    The location and size of nanoscale free-volume holes (nanoholes) in graft-type polymer electrolyte membranes (PEMs), which were prepared by radiation-induced graft polymerization (grafting) of styrene into crosslinked-polytetrafluoroethylene (cPTFE) films and subsequent sulfonation, were investigated using positron annihilation lifetime (PAL) spectroscopy. The PAL spectra of the PEMs indicated the existence of two types of ortho-positronium (o-Ps) species, corresponding to nanoholes with volumes of 0.11 and 0.38 nm3. A comparison of the PAL data of the PEMs with that of the precursor original cPTFE and polystyrene-grafted films demonstrated the probability that the smaller holes were located in both the PTFE crystalline phases and the poly(styrene sulfonic acid) graft regions, whereas the larger holes are potentially localized in the PTFE amorphous phases. Taking into account both the size and the location of the nanoholes, it was concluded that gas transport through the larger holes in the amorphous PTFE phases was dominant over permeation through the smaller holes in the PTFE crystals and grafted regions.

  7. Structure-function properties of amylose-oleic acid inclusion complexes grafted with poly(methyl acrylate)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Spherulites, produced by steam jet-cooking high-amylose starch and oleic acid, were grafted with methyl acrylate, both before and after removal of un-complexed amylopectin. For comparison, granular high-amylose corn starch was graft polymerized in a similar manner. The amount of grafted and ungrafte...

  8. Synthesis of graft polyrotaxane by simultaneous capping of backbone and grafting from rings of pseudo-polyrotaxane.

    PubMed

    Kato, Kazuaki; Inoue, Katsunari; Kudo, Masabumi; Ito, Kohzo

    2014-01-01

    Graft polyrotaxanes, with poly(?-caprolactone) (PCL) graft chains on the ring components were synthesized by the simultaneous ring-opening polymerization of ?-caprolactone from both ends of the backbone polymer, an end-functionalized polyethylene glycol (PEG) and the formation of inclusion complexes with ?-cyclodextrin (?-CD). PEG with multiple functional groups at each end was prepared by the condensation of PEG-amine and D-gluconic acid; the PEG derivative formed an inclusion complex with ?-CD. The polymerization of multiple hydroxy groups at the backbone ends resulted in a star-shaped end group, which served as a bulky capping group to prevent dethreading. In contrast, PEG with only one hydroxy group at each end did not produce polyrotaxanes, indicating that single PCL chains were too thin to confine ?-CDs to the complex. In addition, the grafting polymerization proceeded properly only when robust hydrogen bonds formed between ?-CDs were dissociated using a basic catalyst. Since the dissociation also induced dethreading, kinetic control of the polymerization and dissociation were crucial for producing graft polyrotaxanes. Consequently, this three-step reaction yielded graft polyrotaxanes in a good yield, demonstrating a significant simplification of the synthesis of graft polyrotaxanes. PMID:25383129

  9. Chronic graft-versus-host disease in the rat radiation chimera: I. clinical features, hematology, histology, and immunopathology in long-term chimeras

    SciTech Connect

    Beschorner, W.E.; Tutschka, P.J.; Santos, G.W.

    1982-04-01

    The clinical features, pathology, and immunopathology of chronic graft-versus-host disease (GVHD) developing in the long-term rat radiation chimera are described. At 6 to 12 months post-transplant, the previously stable ACI/LEW chimeras developed patchy to diffuse severe hair loss and thickened skin folds, and had microscopic features resembling scleroderma, Sjogren's syndrome, and chronic hepatitis. Skin histology showed dermal inflammation and acanthosis with atrophy of the appendages, with progression to dermal sclerosis. The liver revealed chronic hepatitis with bile duct injury and proliferation and periportal piecemeal necrosis. The tongue had considerable submucosal inflammation, muscular necrosis, and atrophy and arteritis. The serous salivary glands, lacrimal glands, and bronchi had lymphocytic inflammation and injury to duct, acinar, and mucosal columnar epithelium. The thymus had lymphocyte depletion of the medulla with prominent epithelium. The spleen and lymph nodes had poorly developed germinal centers but increased numbers of plasma cells. IgM was observed along the basement membrane and around the basal cells of the skin and tongue and along the basement membrane of the bile ducts. IgM was present also in the arteries of the tongue. Immunoglobulins eluted from the skin, cross-reacted with the bile duct epithelium and usually with both ACI and Lewis skin. Increased titers of speckled antinuclear antibodies were present in the serum of rats with chronic (GVHD). Chronic GVHD in the long-term rat radiation chimera is very similar to human chronic GVHD and is a potentially excellent model for autoimmune disorders including scleroderma, Sjorgren's syndrome, and chronic hepatitis.

  10. Hydrolases in Polymer Chemistry: Chemoenzymatic Approaches to Polymeric Materials

    NASA Astrophysics Data System (ADS)

    Heise, Andreas; Palmans, Anja R. A.

    Lipases show high activity in the polymerization of a range of monomers using ring-opening polymerization and polycondensation. The range of polymer structures from this enzymatic polymerization can be further increased by combination with chemical methods. This paper reviews the developments of the last 5-8 years in chemoenzymatic strategies towards polymeric materials. Special emphasis is on the synthesis of polymer architectures like block and graft copolymers and polymer networks. Moreover, the combination of chemical and enzymatic catalysis for the synthesis of unique chiral polymers is highlighted.

  11. Radiation grafting of pH-sensitive acrylic acid and 4-vinyl pyridine onto nylon-6 using one- and two-step methods

    NASA Astrophysics Data System (ADS)

    Ortega, Alejandra; Alarcón, Darío; Muñoz-Muñoz, Franklin; Garzón-Fontecha, Angélica; Burillo, Guillermina

    2015-04-01

    Acrylic acid (AAc) and 4-vinyl pyridine (4VP) were γ-ray grafted onto nylon-6 (Ny6) films via pre-irradiation oxidative method. These monomers were grafted using a one-step method to render Ny6-g-(AAc/4VP). A two-step or sequential method was used to render (Ny6-g-AAc)-g-4VP. Random copolymer branches were obtained when the grafting was carried out via one-step method using the two monomers together. The two-step method was applied to graft chains of 4VP on both Ny6 substrate and previously grafted AAc chains (Ny6-g-AAc). The two types of binary copolymers synthesized were characterized to determine the amount of grafted polymers, the thermal behavior (DSC and TGA), the surface composition (XPS), and the pH responsiveness. In the two-step process, it is possible to achieve a higher graft yield, better control of the amount of each monomer, good reversibility in the swelling/deswelling process and shorter time to achieve equilibrium swelling.

  12. Evaluation of a Bovine Vascular Graft in Sheep.

    PubMed

    Knapp, Joseph; Rizzo, Amy; Maxwell, Matt; Duran, Carlos; Cheung, David

    2016-05-01

    The study objective was to determine safety and efficacy of a treated bovine vascular xenograft, in two Good Laboratory Practice compliant studies in sheep following carotid graft implantation. In one study, a 3- to 5-mm diameter xenograft was implanted into the right carotid artery of male sheep and compared to autologous jugular vein and a polymeric grafts similarly implanted. In a second study, a 9.5- to 14-mm diameter xenograft similarly implanted into the right carotid artery was compared to an autologous saphenous vein. Monthly Doppler ultrasound evaluation of implant patency and flow in implants and contralateral control carotid arteries was performed. The small vessel cohort 6 month xenograft patency was equivalent (or better) than animals with polymeric vascular graft or autologous vein implants; the aneurysm incidence was less than that of autologous vein grafts. In the large vessel cohort, all 15 xenografts and 12/15 saphenous vein implants were patent at 6 month follow-up. Tissue histology showed mild inflammatory responses in the xenografts that was slightly greater than suture material. In summary, treated bovine xenograft performance in this small study suggests it may be superior to polymeric autologous vein grafts, and may have a similar failure rate as autologous vein grafts after implantation. PMID:27168579

  13. Biohybrid Branched Copolymers of Controlled Nanostructure Based on Polyacrylamide Grafted to Dextran or Dextran Sulphate Backbone

    NASA Astrophysics Data System (ADS)

    Kutsevol, N.; Soushko, R.; Guenet, J.-M.; Melnyk, N.

    2008-08-01

    Branched polymers Dextran-graft-Polyacrylamide and Dextran Sulphate-graft-Polyacrylamide copolymers with long polysaccharide backbone and various amount and length of PAA-grafts were synthesised by radical polymerization using Ce(IV)/HNO3 redox system. It was established, that these copolymers have expanded conformation in solution and are able to intramolecular structure formation. Grafting efficiency is conditioned by amount of initiator and Dextran (or Dextran Sulphate) conformation in solution. It was shown that increase in content of copolymer Polyacrylamide component in Dextran Sulphate-graft-Polyacrylamide copolymers causes decrease in size of macromolecule due to blocking of polyion charge of main polysaccharide chain by counterions.

  14. Chain Reaction Polymerization.

    ERIC Educational Resources Information Center

    McGrath, James E.

    1981-01-01

    The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

  15. Photoactivated surface grafting from PVDF surfaces

    NASA Astrophysics Data System (ADS)

    Berthelot, Thomas; Le, Xuan Tuan; Jégou, Pascale; Viel, Pascal; Boizot, Bruno; Baudin, Cécile; Palacin, Serge

    2011-09-01

    Economic and easy methods to tune surface properties of polymers as Poly(vinylidene fluoride) (PVDF) without altering bulk properties are of major interest for different applications as biotechnological devices, medical implant device… UV irradiation appears as one of the simplest, easy and safe method to modify surface properties. In the case of self-initiated grafting, it is generally assumed that the pre-treatment of the PVDF surface with UV irradiation can yield alkyl and per-oxy radicals originating from breaking bonds and capable of initiating the subsequent surface grafting polymerizations. Surprisingly, the present work shows that it is possible to obtain polymer grafting using low energetic UV-A irradiation (3.1-3.9 eV) without breaking PVDF bonds. An EPR study has been performed in order to investigate the nature of involved species. The ability of the activated PVDF surface to graft different kinds of hydrophilic monomers using the initiated surface polymerization method has been tested and discussed on the basis of ATR FT-IR, XPS and NMR HRMAS results.

  16. Hemoglobin loaded polymeric nanoparticles: preparation and characterizations.

    PubMed

    Dessy, Alberto; Piras, Anna M; Schirò, Giorgio; Levantino, Matteo; Cupane, Antonio; Chiellini, Federica

    2011-05-18

    In the present work polymeric nanoparticles based on Poly (maleic anhydride-alt-butyl vinyl ether) 5% grafted with m-PEG (2000) and 95% grafted with 2-methoxyethanol (VAM41-PEG) were loaded with human hemoglobin (Hb) and characterized from a physicochemical point of view. The assessment of structural and functional features of the loaded Hb was performed and the effect of the introduction of different reducing agents as aimed at minimizing Hb oxidation during the nanoparticles formulation process, was also investigated. Nanoparticles possessing an average diameter of 138±10 nm and physicochemical features suitable for this kind of application were successfully obtained. Although the oxidation of the protein was not avoided during its loading into nanoparticles, the presence of acidic moieties in the polymeric structure is proposed to be directly involved in the protein inactivation mechanism. PMID:21443949

  17. Preparation and enhanced properties of polyaniline/grafted intercalated ZnAl-LDH nanocomposites

    NASA Astrophysics Data System (ADS)

    Hu, Jinlong; Gan, Mengyu; Ma, Li; Zhang, Jun; Xie, Shuang; Xu, Fenfang; Shen, JiYue Zheng Xiaoyu; Yin, Hui

    2015-02-01

    The polymeric nanocomposites (PANI/AD-LDH) were prepared by in situ polymerization based on polyaniline (PANI) and decavanadate-intercalated and ?-aminopropyltriethoxysilane (APTS)-grafted ZnAl-layered double hydroxide (AD-LDH). FTIR and XRD studies confirm the grafting of APTS with decavanadate-intercalated LDH (D-LDH). The extent of grafting (wt%) has also been estimated on the basis of the residue left in nitrogen atmosphere at 800 C in TGA. SEM and XPS studies show the partial exfoliation of grafted LDH in the PANI matrix and the interfacial interaction between PANI and grafted LDH, respectively. The grafted intercalated layered double hydroxide in reinforcing the properties of the PANI nanocomposites has also been investigated by open circuit potential (OCP), tafel polarization curves (TAF), electrochemical impendence spectroscopy (EIS), salt spray test and TGA-DTA. The experimental results indicate that the PANI/AD-LDH has a higher thermal stability and anticorrosion properties relative to the PANI.

  18. Improved polymer encapsulation on multiwalled carbon nanotubes by selective plasma induced controlled polymer grafting.

    PubMed

    Roy, Sunanda; Das, Tanya; Yue, C Y; Hu, Xiao

    2014-01-01

    Surface graft polymerization on multiwalled carbon nanotubes (MWCNTs) with several grafting mechanisms is nowadays a demanding field of nanocomposites in order to enhance the load carrying capacity, thus improving the overall performance of the composites. Here, we demonstrate the covalent grafting of a sulfonic acid terminated monomer, 2-acrylamido-2-methylpropane sulfonic acid onto sidewalls of MWCNTs via a comparative study between oxygen plasma induced grafting (OPIG), nitrogen plasma induced grafting (NPIG), and nitrogen + oxygen plasma induced grafting (NOPIG) with the aim to identify the most effective process for the preparation of polymer encapsulated carbon nanotubes. From the detail surface analysis, it has been noticed that NOPIG offered much better surface grafting than that of the OPIG and NPIG. The transmission electron microscopy (TEM) images showed that MWCNTs modified by NOPIG possess much thicker and uniform polymer coatings throughout. From thermogravimetric analysis (TGA), the grafting degree was found to be ~80 wt % for the NOPIG sample. PMID:24191852

  19. Electrostrictive Graft Elastomers

    NASA Technical Reports Server (NTRS)

    Su, Ji (Inventor); Harrison, Joycelyn S. (Inventor); St.Clair, Terry L. (Inventor)

    2003-01-01

    An electrostrictive graft elastomer has a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules. The polar graft moieties have been rotated by an applied electric field, e.g., into substantial polar alignment. The rotation is sustained until the electric field is removed. In another embodiment, a process for producing strain in an elastomer includes: (a) providing a graft elastomer having a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules; and (b) applying an electric field to the graft elastomer to rotate the polar graft moieties, e.g., into substantial polar alignment.

  20. Separation of copper ions from iron ions using PVA-g-(acrylic acid/N-vinyl imidazole) membranes prepared by radiation-induced grafting.

    PubMed

    Ajji, Zaki; Ali, Ali M

    2010-01-15

    Acrylic acid (AAc), N-vinyl imidazole (Azol) and their binary mixtures were graft copolymerized onto poly(vinyl alcohol) membranes using gamma irradiation. The ability of the grafted membranes to separate Cu ions from Fe ions was investigated with respect to the grafting yield and the pH of the feed solution. The data showed that the diffusion of copper ions from the feed compartment to the receiver compartment depends on the grafting yield of the membranes and the pH of the feed solution. To the contrary, iron ions did not diffuse through the membranes of all grafting yields. However, a limited amount of iron ions diffused in strong acidic medium. This study shows that the prepared membranes could be considered for the separation of copper ions from iron ions. The temperature of thermal decomposition of pure PVA-g-AAc/Azol membrane, PVA-g-AAc/Azol membrane containing copper ions, and PVA-g-AAc/Azol membrane containing iron ions were determined using TGA analyzer. It was shown that the presence of Cu and Fe ions increases the decomposition temperature, and the membranes bonded with iron ions are more stable than those containing copper ions. PMID:19836882

  1. [Bone grafts (editorial)].

    PubMed

    P?omi?ski, Janusz; Kwiatkowski, Krzysztof

    2006-12-01

    Bone grafts remains the most effective grafting material because it provides the three elements required for bone regeneration: osteoconduction, osteoinduction and osteogenic cells. Bone grafts are used in the repair of significant fractures, the treatment of skeletal tumors and the reconstruction of failed total arthroplasties. Allografts of bone elicit transplantation immunity and this immunogenicity may cause the higher failure rate of these grafts. In an attempt to reduce the immunogenicity of the graft, allogenic bone has been frozen and freeze-dried. Because of increasing clinical use of bone grafts and the unacceptable failure rate, it would be advantageous to better understand the biological response to grafts in order to better define the parameters necessary for a successful bone grafts. PMID:17405286

  2. Polymer Grafted Nanoparticle-based Oil Dispersants

    NASA Astrophysics Data System (ADS)

    Kim, Daehak; Krishnamoorti, Ramanan

    2015-03-01

    Particle-based oil dispersants mainly composed of inorganic nanoparticles such as silica nanoparticles are considered as environmentally friendly oil dispersants due to their biocompatibility and relatively low toxicity. The oil-water interfacial tension is reduced when nanoparticles segregate to the oil-water interface and this segregation is improved by grafting interfacially active polymer brushes. In this study, surfactant-like amphiphilic block copolymers were grafted from silica nanoparticles using an atom transfer radical polymerization (ATRP) method in order to increase their interfacial activity. We have studied the interfacial activity of such hybrid nanoparticles using pendant drop interfacial tension measurements, and their structure using small angle X-ray scattering. Amphiphilic copolymer grafted nanoparticles significantly reduced oil-water interfacial tension compared to the interfacial tension reduction induced by homopolymer grafted nanoparticles or the corresponding free ungrafted copolymer. Moreover, hard and stable oil-water emulsions were formed by applying the block copolymer grafted nanoparticles due to the formation of interparticle network structures, which were observed by cryo-scanning electron microscopy (SEM) and small angle neutron scattering (SANS)

  3. Radial artery graft vasospasm.

    PubMed

    Gabe, E D; Figal, J C; Wisner, J N; Laguens, R

    2001-01-01

    We report an unusual case of vasospasm of a grafted radial artery complicated with ventricular fibrillation during the postoperative course of coronary artery bypass graft surgery. To our knowledge this is the first documented case of a radial artery graft spasm leading to a severe arrhythmia. The arrhythmia resolved spontaneously. Radial artery graft spasm was demonstrated by angiography and was successfully resolved by intravenous nitroglycerin administration. PMID:11163573

  4. Free and microvascular bone grafting in the irradiated dog mandible

    SciTech Connect

    Altobelli, D.E.; Lorente, C.A.; Handren, J.H. Jr.; Young, J.; Donoff, R.B.; May, J.W. Jr.

    1987-01-01

    Microvascular and free rib grafts were placed in 4.5 cm defects in an edentate mandibular body defect 18 to 28 days after completion of 50 Gy of irradiation from a /sup 60/Co source. The animals were sacrificed from two to forty weeks postoperatively and evaluated clinically, radiographically, and histologically. There was a marked difference in the alveolar mucosal viability with the two grafts. Mucosal dehiscence was not observed over any of the microvascular grafts, but was present in seven-eighths of the free grafts. Union of the microvascular bone graft to the host bone occurred within six weeks. In contrast, after six weeks the free graft was sequestered in all the animals. An unexpected finding with both types of graft was the marked subperiosteal bone formation. This bone appeared to be derived from the host bed, stabilizing and bridging the defects bilaterally. The results suggest that radiated periosteum may play an important role in osteogenesis.

  5. Immobilization of Polymeric Luminophor on Nanoparticles Surface

    NASA Astrophysics Data System (ADS)

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-04-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor.

  6. Synthesis of ethylene-propylene rubber graft copolymers by borane approach

    SciTech Connect

    Chung, T.C.; Janvikul, W.; Bernard, R.; Jiang, G.J. . Dept. of Materials Science and Engineering)

    1994-01-01

    This paper describes a new method to prepare graft copolymers which have an EP rubber backbone and several free radical polymerized polymers grafted thereto. The process involves hydroboration of commercial EPDM rubbers, such as poly(ethylene-co-propylene-co-1,4-hexadiene) and poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene), with 9-borabicyclononane (9-BBN). The resulting secondary alkyl-9-BBN moieties in the EPDM copolymer were then exposed to oxygen in the presence of free radical polymerizable monomers. Under certain conditions, the selective autoxidation reaction of secondary alkyl-9-BBN took place to create desirable polymeric radicals which can in situ initiate free radical polymerization. High graft efficiency was observed with controllable copolymer compositions. The graft copolymer of EP-g-PMMA is used to show the chemistry as well as some of the physical properties.

  7. Photoinduced graft-copolymer synthesis and characterization of methacrylic acid onto natural biodegradable lignocellulose fiber.

    PubMed

    Khan, Ferdous

    2004-01-01

    UV radiation induced graft copolymerization of methacrylic acid onto natural lignocellulose (jute) fiber was carried out both by "simultaneous irradiation and grafting" and by preirradiation methods using 1-hydroxycyclohexyl-phenyl ketone as a photoinitiator. In the "simultaneous irradiation and grafting" method, the variation of graft weight with UV-radiation time, monomer concentration, and the concentration of photoinitiator was investigated. In the case of the preirradiation method, the incorporation of 2-methyl-2-propene 1-sulfonic acid, sodium salt, into the grafting reaction solution played a most important role in suppressing the homopolymer/gel formation and facilitating graft copolymerization. The optimum value of the reaction parameters on the percentage of grafting was evaluated. In comparison, results showed that the method of graft-copolymer synthesis has significant influence on graft weight. The study on the mechanical and thermal properties of grafted samples was conducted. The results showed that the percentage of grafting has a significant effect on the mechanical and thermal properties in the case of grafted samples. Considering the water absorption property, the jute-poly(methacrylic acid)-grafted sample showed a maximum up to 42% increase in hydrophilicity with respect to that of the "as received" sample. Attenuated total reflection infrared studies indicate that the estimation of the degree of grafting could be achieved by correlating band intensities with the percent graft weight. PMID:15132702

  8. Synthesis and characterization of carbon fibers functionalized with poly (glycidyl methacrylate) via atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Wu, Yongwei; Xiong, Lei; Qin, Xiaokang; Wang, Zhengyue; Ding, Bei; Ren, Huan; Pi, Xiaolong

    2015-07-01

    In this work, polyacrylonitrile (PAN)-based carbon fibers (CF) were chemically modified with poly (glycidyl methacrylate) (PGMA) via atom transfer radical polymerization (ATRP) to improve the interaction between the CF and polymer matrix. The FT-IR, TGA, and XPS were used to determine the chemical structure of the resulting products and the quantities of PGMA chains grafted from the CF surface. The experimental results confirm that the CF surface was functionalized and glycidyl methacrylate was graft-polymerized onto the CF, and the grafting content of polymer could reach 10.2%.

  9. Polymerization of perfluorobutadiene at near-ambient conditions

    NASA Technical Reports Server (NTRS)

    Toy, M. S.

    1971-01-01

    Peroxide catalyst under mild conditions initiates homopolymerization of perfluoro butadiene to new linear perfluoro polyenes and vulcanizable fluoro elastomers. Resulting polyperfluoro butadiene serves as hard elastomer for good chemical resistance, as intermediate in graft polymerizations, and as crosslink for high molecular weight materials.

  10. Grafting of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole onto polymers with aliphatic groups. Synthesis and polymerization of 2 (2-hydroxy-5-isopropenylphenyl) 2H-benzotriazole and a new synthesis of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole

    NASA Technical Reports Server (NTRS)

    Pradellok, W.; Nir, Z.; Vogl, O.

    1981-01-01

    Successful grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto saturated aliphatic C-H groups of polymers has been accomplished. When the grafting reaction was carried out in chlorobenzene at 150 C = 160 C with di-tertiarybutylperoxide as the grafting initiator, grafts as high as 20 percent - 30 percent at a grafting efficiency of 50 percent and 80 percent have readily been obtained. The grafting reaction was carried out in tubes sealed under high vacuum since trace amounts of oxygen cause complete inhibition of the grafting reaction by the phenolic monomer. On a variety of different polymers including atactic polypropylene, ethylene/vinyl acetate copolymer, poly(methyl methacrylate), poly(butyl acrylate), and polycarbonate were used.

  11. Polymeric Materials for Tissue Engineering of Arterial Substitutes

    PubMed Central

    Ravi, Swathi; Qu, Zheng; Chaikof, Elliot L.

    2009-01-01

    Cardiovascular disease is the leading cause of mortality in the United States. The limited availability of healthy autologous vessels for bypass grafting procedures has led to the fabrication of prosthetic vascular conduits. Synthetic polymeric materials, while providing the appropriate mechanical strength, lack the compliance and biocompatibility that bioresorbable and naturally occurring protein polymers offer. Vascular tissue engineering approaches have emerged in order to meet the challenges of designing a vascular graft with long-term patency. In vitro culture techniques that have been explored with vascular cell seeding of polymeric scaffolds and the use of bioactive polymers for in situ arterial regeneration have yielded promising results. This review describes the development of polymeric materials in various tissue engineering strategies for the improvement in the mechanical and biological performance of an arterial substitute. PMID:19426609

  12. Polymeric materials in Space

    NASA Astrophysics Data System (ADS)

    Skurat, Vladimir

    Paper of short review type. It is the continuation of and addition to previous review papers "V. E. Skurat. Polymers in Space. In: Encyclopedia of aerospace engineering, vol. 4, Wiley and sons, 2010; Ibid., 2012 (on line)". Following topics are considered: (1) Destruction of polymers by solar radiation with various wavelengths in different spectral regions (visible-UV, vacuum UV (VUV), deep UV, soft and hard X-rays) are discussed. In difference with common polymer photochemistry induced by UV radiation, directions of various routs of polymer phototransformations and their relative yields are greatly dependent on wavelength of light (photon energy) during illuminations in VUV, deep UV and X-ray regions. During last twenty years, intensive spacecraft investigations of solar spectrum show great periodic and spontaneous variations of radiation intensities in short-wavelengths regions - up to one - two decimal orders of magnitude for X-rays. As a result, during solar flares the absorbed dose on the polymer surfaces from X-rays can be compared with absorbed dose from VUV radiation. (2) Some new approaches to predictions of reaction efficiencies of fast orbital atomic oxygen in their interaction with polymeric materials are considered. (3) Some aspects of photocatalitic destruction of polymers in vacuum conditions by full-spectrum solar radiation are discussed. This process can take place in enamels containing semiconducting particles (TiO2, ZnO) as pigments. (4) Contamination of spacecraft surfaces from intrinsic outer atmosphere play important role not only from the point of view of deterioration of optical and thermophysical properties. Layers of SiO2 contaminations with nanometer thicknesses can greatly diminish mass losses from perfluorinated polymers under VUV irradiation.

  13. Polymerization of perfluorobutadiene

    NASA Technical Reports Server (NTRS)

    Newman, J.; Toy, M. S.

    1970-01-01

    Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

  14. Thin Film Deformation Behavior of Polystyrene Grafted Nanoparticle Assemblies

    NASA Astrophysics Data System (ADS)

    Jiao, Yang; Hsiao, Ming-Siao; Drummy, Lawrence; Vaia, Richard

    Assemblies of polymer-grafted ``hairy'' nanoparticles (HNPs) are of current interest for a wide array of mechanical, photonic and electrical applications. In contrast to nanoparticles dispersed in a free polymer matrix, the grafted polymer determines particle spacing and circumvents nanoparticle agglomeration. The extent to which these grafted polymers are entangled determines the robustness and strength of the HNP assembly. Here in, we investigate the correlations between grafted polymer conformation, entanglements and deformation mechanisms of thin film assemblies of polystyrene-grafted HNPs by controlling the HNP architecture (grafting density and molecular weight). HNPs with varied corona structures are synthesized with surface-initiated controlled/living radical polymerization. Thin films with controlled thickness are prepared by flow coating. Plastic deformation of thin films are examined using static (bright field, HAADF-STEM, tomography) and AFM techniques. Results show a decrease of void density in craze as grafted polymer length increases for semi-dilute polymer brushes. These correlations between HNP architecture and assembly deformation and failure modes refine the HNP design space for the synthesis and fabrication of assemblies with excellent mechanical properties.

  15. Polymerization Reactor Engineering.

    ERIC Educational Resources Information Center

    Skaates, J. Michael

    1987-01-01

    Describes a polymerization reactor engineering course offered at Michigan Technological University which focuses on the design and operation of industrial polymerization reactors to achieve a desired degree of polymerization and molecular weight distribution. Provides a list of the course topics and assigned readings. (TW)

  16. Evaluation of a cesium adsorbent grafted with ammonium 12-molybdophosphate

    NASA Astrophysics Data System (ADS)

    Shibata, Takuya; Seko, Noriaki; Amada, Haruyo; Kasai, Noboru; Saiki, Seiichi; Hoshina, Hiroyuki; Ueki, Yuji

    2016-02-01

    A fibrous cesium (Cs) adsorbent was developed using radiation-induced graft polymerization with a cross-linked structure containing a highly stable adsorption ligand. The ligand, ammonium 12-molybdophosphate (AMP), was successfully introduced onto the fibrous polyethylene trunk material. The resulting Cs adsorbent contained 36% nonwoven fabric polyethylene (NFPE), 1% AMP, 2% triallyl isocyanurate (TAIC) and 61% glycidyl methacrylate (GMA). The adsorbent's Cs adsorption capacity was evaluated using batch and column tests. It was determined that the adsorbent could be used in a wide pH range. The amount of desorbed molybdenum, which can be used as an estimate for AMP stability on the Cs adsorbent, was minimized at the standard drinking water pH range of 5.8-8.6. Based from the inspection on the adherence of these results to the requirements set forth by the Food Sanitation Act by a third party organization, it can be concluded that the developed Cs adsorbent can be safely utilized for drinking water.

  17. Alveolar bone grafting.

    PubMed

    Semb, Gunvor

    2012-01-01

    In the 1970s, Boyne and Sands published reports on a new technique for alveolar bone grafting. They recommended that only cancellous bone be used and that the procedure be undertaken in the mixed dentition prior to canine eruption. Alveolar bone grafting prior to canine eruption soon became a routine part of the protocol for 90% of European and North American cleft teams. Several uncertainties remain however, such as the specifics of the surgical and orthodontic procedures, type of bone and donor site, and the best way to manage the space in the dental arch. Probably the commonest timing of the bone graft falls between 8 and 11 years, however there has been a trend in some centres to graft earlier in the hope of better outcome for the unerupted incisors. The influence on maxillary growth of earlier grafting has not been ascertained. A wide range of donor sites has been use but iliac crest remains the most popular. Many teams perform orthodontics prior to grafting to correct severe segment displacement or align incisors to improve surgical access. Following grafting, absence of the lateral incisor may be managed with orthodontic space closure, placement of an implant or bridgework. The introduction of alveolar bone grafting probably represents one of the most significant clinical innovations in cleft care. Hopefully, advances in tissue engineering will replace the need for transplantation of autogenous bone, or will provide an in-situ biological solution to the generation of a continuous bone fill across the alveolar cleft. PMID:22759676

  18. Heterogeneous polymerizations in supercritical carbon dioxide continuous phases

    SciTech Connect

    DeSimone, J.M.; Maury, E.E.; Combes, J.R.; Menceloglu, Y.Z.

    1993-12-31

    Heterogeneous emulsion polymerizations are important industrial methods for the synthesis of various polymeric materials. These processes generally use water as the dispersing medium. The authors propose to utilize carbon dioxide as the dispersing medium which would make the polymer recovery easier and would circumvent the contamination of water. In CO{sub 2} - based emulsion process one can have either a hydrophilic dispersed phase (hydrophilic monomer) or a hydrophobic dispersed phase (hydrophobic monomer). The surfactant has to be designed to partition itself at the CO{sub 2} - monomer/polymer interface and the initiator has to be soluble in the dispersing medium. The design of the initiator and graft copolymer surfactants will be presented. One example of a graft copolymer is a copolymer of poly(ethylene oxide) macromonomer synthesized by living anionic polymerization and a fluoroacrylate monomer resulting in a graft copolymer having hydrophilic grafts and a {open_quotes}CO{sub 2}-philic{close_quotes} backbone (due to the fluorine chains). The phase behavior of these surfactants will be discussed at the meeting.

  19. Radiation chemical modification of rubbers on the basis of ethylene-propylene terpolymer and butadiene-styrene thermoelastoplastic

    NASA Astrophysics Data System (ADS)

    Pikaev, A. K.; Shemenkova, L. V.; Timofeeva, V. F.; Glazunov, P. Ya.

    With the purpose of improving the operating characteristics of rubbers on the basis of ethylene-propylene terpolymer and butadiene-styrene thermoelastoplastic their modification by radiation graft polymerization of acrylic monomers (acrylonitrile, acrylic acid, glycidyl methacrylate, cyanoethyl methacrylate etc.) was carried out. The investigations performed made it possible to select monomers, whose grafting onto rubbers improves the adhesion properties and increases oil resistance of the latter. A continuous grafting process by the method of impregnation of rubber with monomer using a pilot plant with an electron accelerator was developed. The output of the pilot plant at a dose rate of 2.2 kGy/s is 4.2 t/year.

  20. Grafts in "closed" rhinoplasty.

    PubMed

    Scattolin, A; D'Ascanio, L

    2013-06-01

    Rhinoplasty is a fascinating and complex surgical procedure aiming at attaining a well-functioning and aesthetically pleasant nose. The use of grafts is of the utmost importance for the nasal surgeon to achieve such results. However, the philosophy and technical use of nasal grafts are different in "closed" and "open" rhinoplasty. The aim of this paper is not detailed description of the numerous grafts reported in the literature; we will describe the main principles of grafts use in "closed" rhinoplasty derived from our experience, with special reference to the philosophical and technical differences in their employment between "closed" and "open" rhinoplasty. Some cases are reported as an example of graft use in "endonasal" approach rhinoplasty. PMID:23853412

  1. A Versatile Star PEG Grafting Method for the Generation of Nonfouling and Nonthrombogenic Surfaces

    PubMed Central

    Thalla, Pradeep Kumar; Contreras-García, Angel; Fadlallah, Hicham; Barrette, Jérémie; De Crescenzo, Gregory; Merhi, Yahye; Lerouge, Sophie

    2013-01-01

    Polyethylene glycol (PEG) grafting has a great potential to create nonfouling and nonthrombogenic surfaces, but present techniques lack versatility and stability. The present work aimed to develop a versatile PEG grafting method applicable to most biomaterial surfaces, by taking advantage of novel primary amine-rich plasma-polymerized coatings. Star-shaped PEG covalent binding was studied using static contact angle, X-ray photoelectron spectroscopy (XPS), and quartz crystal microbalance with dissipation monitoring (QCM-D). Fluorescence and QCM-D both confirmed strong reduction of protein adsorption when compared to plasma-polymerized coatings and pristine poly(ethyleneterephthalate) (PET). Moreover, almost no platelet adhesion was observed after 15 min perfusion in whole blood. Altogether, our results suggest that primary amine-rich plasma-polymerized coatings offer a promising stable and versatile method for PEG grafting in order to create nonfouling and nonthrombogenic surfaces and micropatterns. PMID:23509823

  2. Protein adsorption and platelet adhesion onto polyurethane grafted with methoxy-poly(ethylene glycol) methacrylate by plasma technique.

    PubMed

    Fujimoto, K; Inoue, H; Ikada, Y

    1993-12-01

    Graft polymerization of methoxy-poly(ethylene glycol) methacrylate, an ester of methacrylic acid and monomethoxy-poly(ethylene glycol) (PEO), was performed onto a polyetherurethane (PU) film and tube under different polymerization conditions by a plasma treatment technique. The surface of grafted PU film was characterized by staining with dye, x-ray photoelectron spectroscopy, contact angle, and zeta potential. All these measurements indicated that water-soluble chains were immobilized on the PU surface, their location being restricted to the film surface region. The PU surface showed reduced protein adsorption in vitro and reduced platelet adhesion in vitro and ex vivo. The optimum graft density suppressing the protein adsorption was as low as 5 micrograms cm(-2). When a small amount of dimethacrylate was added to the monomer solution for graft polymerization to introduce crosslinking in the grafted layer, protein adsorption was further slightly reduced. The extent of reduction in serum albumin adsorption was always less than that of gamma-globulin. Although platelet adhesion was largely reduced by the surface graft polymerization, a definite amount of protein was always adsorbed to the grafted surface. PMID:8113244

  3. Do Stem Cells Have an Effect When We Fat Graft?

    PubMed

    Rinker, Brian D; Vyas, Krishna S

    2016-06-01

    Fat grafting has become a widely accepted modality of soft tissue restoration and has found applications in many areas of aesthetic and reconstructive plastic surgery. Numerous claims have been made regarding the regenerative effects of fat grafting on the recipient bed. The purpose of this paper is to survey the available literature to answer the question of whether fat grafting has a positive effect on the surrounding tissues. It has been convincingly demonstrated that fat grafts contain viable adipose-derived stem cells (ASCs). The fate of these cells is determined by the microenvironment of the recipient bed, but animal studies have shown that a large fraction of ASCs survive engraftment. Numerous clinical studies have demonstrated the positive effects of fat grafting on recipient tissues. Improvement in validated scar scores as well as scar stiffness measurements have been documented after fat grafting of burn scars. Fat grafting has also been convincingly demonstrated to improve the quality of irradiated tissues, as measured by validated clinical scales and staged histology. It is ultimately unclear whether ASCs are responsible for these effects, but the circumstantial evidence is weighty. Fat grafting is effective for volumizing and improving skin quality in the setting of radiation, burns, and other scars. The observed effects are likely due to ASCs, but the evidence does not support the routine use of ASC-enriched fat grafts. PMID:26545225

  4. Ferritin-Polymer Conjugates: Grafting Chemistry and Integration into Nanoscale Assemblies

    SciTech Connect

    Y Hu; D Samanta; S Parelkar; S Hong; Q Wang; T Russell; T Emrick

    2011-12-31

    Controlled free radical polymerization chemistry is used to graft polymer chains to the corona of horse spleen ferritin (HSF) nanocages. Specifically, poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), in which the molecular weight of the polymer grafts is controlled by the monomer-to-initiator feed ratio. PolyMPC and polyPEGMA-grafted ferritin show a generally suppressed inclusion into diblock copolymer films relative to native ferritin, and the polymer coating is seen to mask the ferritin nanocages from antibody recognition. The solubility of polyPEGMA-coated ferritin in organic solvents enables its processing with polystyrene-block-poly(ethylene oxide) copolymers, and selective integration into the PEO domains of microphase-separated copolymer structures.

  5. Infrainguinal anastomotic arterial graft infections treated by selective graft preservation.

    PubMed Central

    Calligaro, K D; Westcott, C J; Buckley, R M; Savarese, R P; DeLaurentis, D A

    1992-01-01

    The purpose of this study was to determine whether the type of graft material and bacteria involved in an infrainguinal arterial anastomotic infection can be used as guidelines for graft preservation. Between 1972 and 1990, the authors treated 35 anastomotic infections involving a common femoral or distal artery. The graft material was Dacron in 14 patients, polytetrafluoroethylene (PTFE) in 14, and vein in 7. Of the 14 Dacron grafts, immediate graft excision was required for overwhelming infection in eight patients (bleeding in five, sepsis in three) and for an occluded graft in one patient. Three of five patients failed attempted graft preservation because of nonhealing wounds. Thus, 12 of the 14 Dacron grafts ultimately required graft excision. Of the 21 "smooth-walled" vein and PTFE grafts, 10 required immediate graft excision for occluded grafts (five PTFE, one vein) or bleeding (three PTFE, one vein). Ten of the remaining 11 (91%) patients with patent "smooth-walled" grafts, intact anastomoses, and absence of sepsis managed by graft preservation healed their wounds and maintained distal arterial perfusion. Wound cultures grew pure gram-positive cocci in 17 of 21 "smooth-walled" graft infections versus 8 of 14 Dacron graft infections. In the absence of systemic sepsis, graft preservation is the treatment of choice for gram-positive infections involving an intact anastomosis of patent PTFE and vein grafts. Regardless of the bacterial cause, the authors recommend that any infrainguinal anastomotic infection of a Dacron graft be treated by immediate excision of all infected graft material. PMID:1632705

  6. Synthesis of polycaprolactone-grafted microfibrillated cellulose for use in novel bionanocomposites--influence of the graft length on the mechanical properties.

    PubMed

    Lönnberg, Hanna; Larsson, Karolina; Lindström, Tom; Hult, Anders; Malmström, Eva

    2011-05-01

    In the present work, microfibrillated cellulose (MFC) made from bleached sulfite softwood dissolving pulp was utilized to reinforce a poly(ε-caprolactone) (PCL) biopolymer matrix. To improve the dispersibility of the hydrophilic MFC in the nonpolar matrix and the interfacial adhesion in the composite material, we covalently grafted the MFC with PCL via ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). To be able to investigate the effect of the PCL graft length on the mechanical properties of the composite material, we performed ROP to different molecular weights of the grafts. Bionanocomposites containing 0, 3, and 10 wt % MFC were prepared via hot pressing using both unmodified and PCL grafted MFC (MFC-g-PCL) as reinforcement. PCL grafting resulted in improved dispersion of the MFC in a nonpolar solvent and in the PCL matrix. The mechanical testing of the biocomposites showed an improvement in the mechanical properties for the PCL grafted MFC in comparison to ungrafted MFC. It was also shown that there was an impact on the mechanical properties with respect to the PCL graft lengths, and the strongest biocomposites were obtained after reinforcement with MFC grafted with the longest PCL graft length. PMID:21473594

  7. Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

    NASA Astrophysics Data System (ADS)

    He, Chunli; Wang, Miao; Cai, Xianmei; Huang, Xiaobo; Li, Li; Zhu, Haomiao; Shen, Jian; Yuan, Jiang

    2011-11-01

    To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm2 for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.

  8. Controlled atom transfer radical polymerization of MMA onto the surface of high-density functionalized graphene oxide

    NASA Astrophysics Data System (ADS)

    Kumar, Mukesh; Chung, Jin Suk; Hur, Seung Hyun

    2014-07-01

    We report on the grafting of poly(methyl methacrylate) (PMMA) onto the surface of high-density functionalized graphene oxides (GO) through controlled radical polymerization (CRP). To increase the density of surface grafting, GO was first diazotized (DGO), followed by esterification with 2-bromoisobutyryl bromide, which resulted in an atom transfer radical polymerization (ATRP) initiator-functionalized DGO-Br. The functionalized DGO-Br was characterized by X-ray photoelectron spectroscopy (XPS), Raman, and XRD patterns. PMMA chains were then grafted onto the DGO-Br surface through a `grafting from' technique using ATRP. Gel permeation chromatography (GPC) results revealed that polymerization of methyl methacrylate (MMA) follows CRP. Thermal studies show that the resulting graphene-PMMA nanocomposites have higher thermal stability and glass transition temperatures ( T g) than those of pristine PMMA.

  9. Controlled atom transfer radical polymerization of MMA onto the surface of high-density functionalized graphene oxide

    PubMed Central

    2014-01-01

    We report on the grafting of poly(methyl methacrylate) (PMMA) onto the surface of high-density functionalized graphene oxides (GO) through controlled radical polymerization (CRP). To increase the density of surface grafting, GO was first diazotized (DGO), followed by esterification with 2-bromoisobutyryl bromide, which resulted in an atom transfer radical polymerization (ATRP) initiator-functionalized DGO-Br. The functionalized DGO-Br was characterized by X-ray photoelectron spectroscopy (XPS), Raman, and XRD patterns. PMMA chains were then grafted onto the DGO-Br surface through a ‘grafting from’ technique using ATRP. Gel permeation chromatography (GPC) results revealed that polymerization of methyl methacrylate (MMA) follows CRP. Thermal studies show that the resulting graphene-PMMA nanocomposites have higher thermal stability and glass transition temperatures (Tg) than those of pristine PMMA. PMID:25114639

  10. Design of modified plastic surfaces for antimicrobial applications: Impact of ionizing radiation on the physical and mechanical properties of polypropylene

    NASA Astrophysics Data System (ADS)

    Riquet, Anne-Marie; Delattre, Jennifer; Vitrac, Olivier; Guinault, Alain

    2013-10-01

    Surface modification of polypropylene (PP) sheets was carried out by radiation induced graft polymerization of hydrophilic functional molecules such as N,N-dimethylacrylamide (DMA) and [2-methacryloyloxy)ethyl] trimethylammonium chloride, which is a quaternary ammonium salt (QAS). Polypropylene sheets were activated prior to the grafting reaction by using electron beam radiation. The changes in morphology, crystallinity and tensile parameters like deformation and stress at yield and deformation at break of PP after irradiation were investigated. The results showed that a minor crystalline reorganization takes place during the irradiation of PP at 100 kGy. The grafting has been observed to be strongly dependent on the monomer dilution in the reaction medium. After grafting of QAS (40%) and DMA (20%) it was possible to develop highly hydrophilic surfaces (water contact angle comprised between 30 and 41°). The surfaces of virgin, irradiated and grafted PP were studied using polarized optical microscopy (POM) and scanning electron microscopy (SEM). Spherical particles (i.e. polystyrene or silica beads) adhering to the modified samples were studied according to the surface parameters. Adhesion tests confirmed the strong influence of substrate type (mainly hydrophilicity and roughness) and to a lesser extent underlined the role of electrostatic interactions for the design of plastic surfaces for antimicrobial applications.

  11. Superhydrophocity via gas-phase monomers grafting onto carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zha, Jinlong; Batisse, Nicolas; Claves, Daniel; Dubois, Marc; Frezet, Lawrence; Kharitonov, Alexander P.; Alekseiko, Leonid N.

    2016-05-01

    Superhydrophobic films were prepared using dispersions of fluorinated multi-walled carbon nanotubes (MWCNTs) or nanofibers (CNFs) in toluene. The grafting of polystyrene allowed stable dispersions to be obtained. The grafting of polystyrene (PS), polyacrylic acid (PAA) and polyaniline (PANI) onto nanofibers and MWCNTs was first evidenced by solid state NMR and Infrared Spectroscopy. The graft polymerization of styrene, acrylic acid and aniline monomers was initiated by radicals (dangling bonds) formed due to the initial fluorination. The process appeared as highly versatile and efficient for different polymers. The consumption of those radicals in the course of grafting was evidenced by EPR, through decrease of the spin density. The hydrophobic/hydrophilic character was tuned according to the grafted polymer nature, i.e. hydrophobic with PS or hydrophilic with PAA. Finally, in order to reach superhydrophobicity, films were prepared from CNFs or MWCNTs, irrespective of their average diameter, that allowed adequate structuring of the surface. The presence of fluorine atoms on their surface also favors superhydrophobicity. Water contact angles of 155 ± 2° and 159 ± 2° were measured for the films casted from fluorinated CNFs or MWCNTs with grafted polystyrene, respectively.

  12. High compliance vascular grafts based on semi-interpenetrating networks

    PubMed Central

    Dempsey, David K.; Nezarati, Roya M.; Mackey, Calvin E.

    2014-01-01

    Current synthetic vascular grafts have poor patency rates in small diameter applications (<6 mm) due to intimal hyperplasia arising from a compliance mismatch between the graft and native vasculature. Enormous efforts have focused on improving biomechanical properties; however, polymeric grafts are often constrained by an inverse relationship between burst pressure and compliance. We have developed a new, semi-interpenetrating network (semi-IPN) approach to improve compliance without sacrificing burst pressure. The effects of heat treatment on graft morphology, fiber architecture, and resultant biomechanical properties are presented. In addition, biomechanical properties after equilibration at physiological temperature were investigated in relation to polyurethane microstructure to better predict in vivo performance. Compliance values as high as 9.2 2.7 %/mmHg x 10?4 were observed for the semi-IPN graft while also maintaining high burst pressure, 1780 230 mm Hg. The high compliance of these heat-treated poly(carbonate urethane) (PCU) and semi-IPN grafts is expected to improve long-term patency rates beyond even saphenous vein autografts by preventing intimal hyperplasia. The fundamental structure-property relationships gained from this work may also be utilized to advance biomedical device designs based on thermoplastic polyurethanes. PMID:25601822

  13. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  14. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  15. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  16. 21 CFR 872.6070 - Ultraviolet activator for polymerization.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... ultraviolet radiation intended to polymerize (set) resinous dental pit and fissure sealants or restorative... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ultraviolet activator for polymerization. 872.6070... (CONTINUED) MEDICAL DEVICES DENTAL DEVICES Miscellaneous Devices § 872.6070 Ultraviolet activator...

  17. Insitu grafting silica nanoparticles reinforced nanocomposite hydrogels

    NASA Astrophysics Data System (ADS)

    Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang; Xu, Feng; Sun, Run-Cang

    2013-10-01

    Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties.Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties. Electronic supplementary information (ESI) available: FTIR spectra of SNP after silane treatment, dynamic oscillatory shear measurements as a function of frequency, constrained polymer chain analysis by a change in the peak height in loss factor spectra, molecular weight of grafted chains at different stages of gelation, prediction of the SNP reinforcing mechanism in the frame of the percolation model, cyclic tensile loading-loading behaviors of SNP gels, and the tearing test. See DOI: 10.1039/c3nr04252a

  18. Bone Graft Alternatives

    MedlinePlus

    ... cadavers. The types of allograft bone used for spine surgery include fresh frozen and lyophilized (freeze dried). The ... the most common uses of bone grafts in spine surgery is during spinal fusion. The use of autogenous ...

  19. Vein graft failure

    PubMed Central

    Owens, Christopher D.; Gasper, Warren J.; Rahman, Amreen S.; Conte, Michael S

    2013-01-01

    Following the creation of an autogenous lower extremity bypass graft, the vein must undergo a series of dynamic structural changes to stabilize the arterial hemodynamic forces. These changes, commonly referred to as remodeling, include an inflammatory response, the development of a neointima, matrix turnover, and cellular proliferation and apoptosis. The sum total of these processes results in dramatic alterations in the physical and biomechanical attributes of the arterialized vein. The most clinically obvious and easily measured of these is lumen remodeling of the graft. However, though somewhat less precise, wall thickness, matrix composition, and endothelial changes can be measured in vivo within the healing vein graft. Recent translational work has demonstrated the clinical relevance of remodeling as it relates to vein graft patency and the systemic factors influencing it. By correlating histologic and molecular changes in the vein, insights into potential therapeutic strategies to prevent bypass failure and areas for future investigation are explored. PMID:24095042

  20. Controlled polymer grafting on single clay nanoplatelets.

    PubMed

    Viville, Pascal; Lazzaroni, Roberto; Pollet, Eric; Alexandre, Michaël; Dubois, Philippe

    2004-07-28

    We report on the controlled chemical grafting of well-defined polymer chains onto individual montmorillonite-type clay nanoplatelets and the direct visualization of the formed hybrid material at the nanoscale level. Our approach is based on the use of a surfactant mixture that contains varying proportions of hydroxyl-substituted alkylammonium and unsubstituted alkylammonium cations to exchange the initial Na(+) counterions of the natural montmorillonite. This allows for the exchange of Na(+) by a tunable amount of hydroxyl functions at the surface of the clays. Those functions are then derivatized into aluminum alkoxides in order to initiate the ring-opening polymerization of epsilon-caprolactone directly from the clay surface that was swollen in an organic solvent. Atomic force microscopy measurements on the resulting polymer-grafted nanoplatelets demonstrate the strong dependence of the coating of the individual clay particles with the composition of the surfactant mixture used for the cationic exchange. This allows for the generation of a range of morphologies varying from polymer islands distributed over the clay surface to homogeneous polymer layers thoroughly coating the platelets. Finally, the control that is achievable over the synthesis of this new family of organic-inorganic nanohybrid materials has been extended to the surface grafting of semicrystalline poly(epsilon-caprolactone)-poly(lactic acid) diblock copolymers with defined compositions. PMID:15264832

  1. Sizing of crimped Dacron grafts.

    PubMed

    Reid, J D; Sladen, J G

    1992-05-01

    The aim of this study was to correlate the stated size of Dacron grafts (Microvel) with their actual internal diameter and to compare this with measurements by ultrasound in the early postoperative period. Grafts of stated diameters of 7, 8, 9, and 10 mm were studied. Grafts were measured by graded probes and by measuring the width of the longitudinally opened graft and calculating the diameter. Each graft accepted a probe 1 mm larger than its stated size very easily and 2 mm greater when stretched. By open measurement, the grafts were 1.3 to 1.8 mm greater than their stated diameter without stretching. Twenty grafts were studied by duplex ultrasound for diameter and peak systolic velocity within 3 months of implantation. The grafts were 12% larger than their stated graft size. Some of the larger grafts showed low velocity and wall thrombus. We conclude that Microvel grafts are larger than their stated diameter. The same size discrepancy was seen in in vitro measurements of Vascutek (Dacron) grafts but not in polytetrafluoroethylene (Gortex) grafts. Since flow velocity is related to the diameter of the graft, this information should be useful when choosing the diameter of a prosthetic vascular graft. PMID:1533494

  2. Ovarian and Uterine Grafts

    PubMed Central

    Cheval, Max

    1934-01-01

    Recent experience has convinced the author of the value of ovarian grafting. He gives the histories of a number of women upon whom he made implants of their own ovarian tissue in the course of operations for double oöphorectomy. The subsequent state of these patients is contrasted with that of women after castration without grafting. When the uterus was left in position menstruation was re-established in over 80% of the grafted cases. The author and his co-workers maintain that the vitality of autogenous grafts of ovarian substance is enhanced by hormones produced by the uterine mucosa. He therefore advocates that grafts of uterus be made in conjunction with ovarian implants whenever possible. Experiments carried out on animals have proved the correctness of this opinion. The results of a series of cases of combined ovarian and uterine graftings are recorded, and the technique of uterine mucosa implants is described. ImagesFig. 10Fig. 11Fig. 1Fig. 2Fig. 3Fig. 4Fig. 8Fig. 9Fig. 10Fig. 5Fig. 6 PMID:19989930

  3. Calcium carbonate crystallization in the presence of modified polysaccharides and linear polymeric additives

    NASA Astrophysics Data System (ADS)

    Matahwa, H.; Ramiah, V.; Sanderson, R. D.

    2008-10-01

    Crystallization of calcium carbonate was performed in the presence of grafted polysaccharides, polyacrylamide (PAM) and polyacrylic acid (PAA). The grafted polysaccharides gave crystal morphologies that were different from the unmodified polysaccharides but similar to the ones given by homopolymers of the grafted chains. PAM-grafted α-cellulose gave rectangular platelets that aggregated to form 'spherical' crystals on the surface of the fiber, whereas PAA grafted α-cellulose gave spherical crystals on the surface of the fiber. X-ray diffraction (XRD) spectroscopy showed that PAM-grafted α-cellulose, PAM as well as the control (no polymeric additive) gave calcite crystals at both 25 and 80 °C. However, the PAA-grafted α-cellulose and PAA homopolymer gave calcite and vaterite crystals at 25 °C with calcite and aragonite crystals along with traces of vaterite being formed at 80 °C. The fiber surface coverage by these crystals was more on the acrylic- and acrylamide-grafted cellulose than on the ungrafted α-cellulose. The evolution of CaCO 3 polymorphs as well as crystal morphology in PAA-grafted starch was similar to that of PAA-grafted α-cellulose at the two temperatures employed.

  4. Phase Behavior and Significantly Enhanced Toughness in Polylactide Graft Copolymers

    NASA Astrophysics Data System (ADS)

    Robertson, Megan; Theryo, Grayce; Jing, Feng; Hillmyer, Marc

    2011-03-01

    Polylactide (PLA), a biodegradable polyester derived from plant sugars, is commercially available and used in a variety of applications ranging from serviceware to resorbable sutures. One limitation to diversifying the applications of the material is its inherent brittleness. Graft copolymers containing PLA arms and a rubbery aliphatic polymer backbone were synthesized by a combination of ring-opening metathesis and ring-opening transesterification polymerizations. The high degree of incompatibility between the arms and backbone resulted in microphase separation of the graft copolymer at increasingly low fractions of the backbone polymer, as evidenced by small-angle x-ray scattering. In graft copolymers with a rubbery content of only 5 wt percent, the tensile strain at break was observed to be as high as twenty times that of neat PLA. Studies are underway to provide insight into the critical polymer molecular parameters for enhanced toughness and the deformation mechanisms.

  5. Toward living radical polymerization.

    PubMed

    Moad, Graeme; Rizzardo, Ezio; Thang, San H

    2008-09-01

    Radical polymerization is one of the most widely used processes for the commercial production of high-molecular-weight polymers. The main factors responsible for the preeminent position of radical polymerization are the ability to polymerize a wide array of monomers, tolerance of unprotected functionality in monomer and solvent, and compatibility with a variety of reaction conditions. Radical polymerization is simple to implement and inexpensive in relation to competitive technologies. However, conventional radical polymerization severely limits the degree of control that researchers can assert over molecular-weight distribution, copolymer composition, and macromolecular architecture. This Account focuses on nitroxide-mediated polymerization (NMP) and polymerization with reversible addition-fragmentation chain transfer (RAFT), two of the more successful approaches for controlling radical polymerization. These processes illustrate two distinct mechanisms for conferring living characteristics on radical polymerization: reversible deactivation (in NMP) and reversible or degenerate chain transfer (in RAFT). We devised NMP in the early 1980s and have exploited this method extensively for the synthesis of styrenic and acrylic polymers. The technique has undergone significant evolution since that time. New nitroxides have led to faster polymerization rates at lower temperatures. However, NMP is only applicable to a restricted range of monomers. RAFT was also developed at CSIRO and has proven both more robust and more versatile. It is applicable to the majority of monomers subject to radical polymerization, but the success of the polymerization depends upon the selection of the RAFT agent for the monomers and reaction conditions. We and other groups have proposed guidelines for selection, and the polymerization of most monomers can be well-controlled to provide minimal retardation and a high fraction of living chains by using one of just two RAFT agents. For example, a tertiary cyanoalkyl trithiocarbonate is suited to (meth)acrylate, (meth)acrylamide, and styrenic monomers, while a cyanomethyl xanthate or dithiocarbamate works with vinyl monomers, such as vinyl acetate or N-vinylpyrrolidone. With the appropriate choice of reagents and polymerization conditions, these reactions possess most of the attributes of living polymerization. We have used these methods in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, including microgels and polymer brushes. Applications of these polymers include novel surfactants, dispersants, coatings and adhesives, biomaterials, membranes, drug-delivery media, electroactive materials, and other nanomaterials. PMID:18700787

  6. Halley's polymeric organic molecules

    NASA Technical Reports Server (NTRS)

    Huebner, W. F.; Boice, D. C.; Korth, A.

    1989-01-01

    The detection of polymeric organic compounds in the mass spectrum of Comet Halley obtained with the Positive Ion Cluster Composition analyzer on Giotto are examined. It is found that, in addition to polyoxymethylene, other polymers and complex molecules may exist in the comet. It is suggested that polymerized hydrogen cyanide may be a source for the observed CN and NH2 jets.

  7. Halley's polymeric organic molecules

    SciTech Connect

    Huebner, W.F.; Boice, D.C.; Korth, A.

    1989-01-01

    The detection of polymeric organic compounds in the mass spectrum of Comet Halley obtained with the Positive Ion Cluster Composition analyzer on Giotto are examined. It is found that, in addition to polyoxymethylene, other polymers and complex molecules may exist in the comet. It is suggested that polymerized hydrogen cyanide may be a source for the observed CN and NH2 jets. 31 refs.

  8. Step-Growth Polymerization.

    ERIC Educational Resources Information Center

    Stille, J. K.

    1981-01-01

    Following a comparison of chain-growth and step-growth polymerization, focuses on the latter process by describing requirements for high molecular weight, step-growth polymerization kinetics, synthesis and molecular weight distribution of some linear step-growth polymers, and three-dimensional network step-growth polymers. (JN)

  9. Cyclic Graft Copolymer Unimolecular Micelles: Effects of Cyclization on Particle Morphology and Thermoresponsive Behavior

    PubMed Central

    2016-01-01

    The synthesis of cyclic amphiphilic graft copolymers with a hydrophobic polycarbonate backbone and hydrophilic poly(N-acryloylmorpholine) (PNAM) side arms via a combination of ring-opening polymerization (ROP), cyclization via copper-catalyzed azide–alkyne cycloaddition (CuAAC), and reversible addition–fragmentation chain transfer (RAFT) polymerization is reported. The ability of these cyclic graft copolymers to form unimolecular micelles in water is explored using a combination of light scattering, small-angle X-ray scattering (SAXS), and cryogenic transmission electron microscopy (cryoTEM) analyses, where particle size was found to increase with increasing PNAM arm length. Further analysis revealed differences in the solution conformations, loading capabilities, and morphologies of the cyclic graft copolymers in comparison to equivalent linear graft copolymer unimolecular micelle analogues. Furthermore, the cyclic and linear graft copolymers were found to exhibit significantly different cloud point temperatures. This study highlights how subtle changes in polymer architecture (linear graft copolymer versus cyclic graft copolymer) can dramatically influence a polymer’s nanostructure and its properties. PMID:27175037

  10. Flame retardant brominated styrene-based polymers. VI. Synthesis and characterization of dibromostyrene graft latices

    SciTech Connect

    Favstritsky, N.A.; Wang, J.L.

    1995-12-01

    Nine dibromostyrene-grafted commercial lattices were prepared in 8 oz bottles by an emulsion polymerization technique. Proper selection of lattices used in conjunction with the dibromostyrene monomer enables production of flame retardant latex products useful in a wide range of coating applications. The prime factor to be considered in the choice of a latex or a latex mixture to be grafted is the glass transition temperature(s) of the polymer(s) in the final latex desired. Lattices chosen for grafting are commercial lattices, such as Rhoplex HA-24 and HA-8, Hystretch V-29, Airflex 465, 4500, 4514 and 4530, Pliolite SBR latex and polybutadiene latex. The graft latex was characterized in terms of glass transition temperature, solids content, bromine content, grafted dibromostyrene and flame retardancy.

  11. Hydrophobic grafted and cross-linked starch nanoparticles for drug delivery.

    PubMed

    Simi, C K; Emilia Abraham, T

    2007-05-01

    The synthesis of modified hydrophobic starch nanoparticles using long chain fatty acids was accomplished. Grafting of fatty acid on the starch was done using potassium persulphate as catalyst and the formation of graft polymer was confirmed by FTIR spectra. The thermal properties of the native and grafted starch were investigated using simultaneous TG-DTA and DSC. The graft polymerization was found to be depending on the temperature and the duration of the reaction. The modified starch nanoparticles were cross-linked with sodium tripoly phosphate for better stabilization. Morphology of the grafted starch nanoparticles was studied by SEM and AFM. Drug-loading and the controlled release of the drug from the nanoparticles was studied using indomethacin as model drug. PMID:17278045

  12. Immobilization of Polymeric Luminophor on Nanoparticles Surface.

    PubMed

    Bolbukh, Yuliia; Podkoscielna, Beata; Lipke, Agnieszka; Bartnicki, Andrzej; Gawdzik, Barbara; Tertykh, Valentin

    2016-12-01

    Polymeric luminophors with reduced toxicity are of the priorities in the production of lighting devices, sensors, detectors, bioassays or diagnostic systems. The aim of this study was to develop a method of immobilization of the new luminophor on a surface of nanoparticles and investigation of the structure of the grafted layer. Monomer 2,7-(2-hydroxy-3-methacryloyloxypropoxy)naphthalene (2,7-NAF.DM) with luminophoric properties was immobilized on silica and carbon nanotubes in two ways: mechanical mixing with previously obtained polymer and by in situ oligomerization with chemisorption after carrier's modification with vinyl groups. The attached polymeric (or oligomeric) surface layer was studied using thermal and spectral techniques. Obtained results confirm the chemisorption of luminophor on the nanotubes and silica nanoparticles at the elaborated synthesis techniques. The microstructure of 2,7-NAF.DM molecules after chemisorption was found to be not changed. The elaborated modification approach allows one to obtain nanoparticles uniformly covered with polymeric luminophor. PMID:27090657

  13. Grafting Technique to Eliminate Rootstock Suckering of Grafted Tomatoes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable grafting has been proposed as a technique for avoiding disease problems in tomatoes in open field production. In this study we investigated the current use of grafting in an open field scenario and found a serious problem with the grafting techniques. In the Fall of 2007, commercially pr...

  14. Grafts for Ridge Preservation

    PubMed Central

    Jamjoom, Amal; Cohen, Robert E.

    2015-01-01

    Alveolar ridge bone resorption is a biologic phenomenon that occurs following tooth extraction and cannot be prevented. This paper reviews the vertical and horizontal ridge dimensional changes that are associated with tooth extraction. It also provides an overview of the advantages of ridge preservation as well as grafting materials. A Medline search among English language papers was performed in March 2015 using alveolar ridge preservation, ridge augmentation, and various graft types as search terms. Additional papers were considered following the preliminary review of the initial search that were relevant to alveolar ridge preservation. The literature suggests that ridge preservation methods and augmentation techniques are available to minimize and restore available bone. Numerous grafting materials, such as autografts, allografts, xenografts, and alloplasts, currently are used for ridge preservation. Other materials, such as growth factors, also can be used to enhance biologic outcome. PMID:26262646

  15. Alveolar bone grafting

    PubMed Central

    Lilja, Jan

    2009-01-01

    In patients with cleft lip and palate, bone grafting in the mixed dentition in the residual alveolar cleft has become a well-established procedure. The main advantages can be summarised as follows: stabilisation of the maxillary arch; facilitation of eruption of the canine and sometimes facilitation of the lateral incisor eruption; providing bony support to the teeth adjacent to the cleft; raising the alar base of the nose; facilitation of closure of an oro-nasal fistula; making it possible to insert a titanium fixture in the grafted site and to obtain favourable periodontal conditions of the teeth within and adjacent to the cleft. The timing of the ABG surgery take into consideration not only eruption of the canine but also that of the lateral incisor, if present. The best time for bone grafting surgery is when a thin shell of bone still covers the soon erupting lateral incisor or canine tooth close to the cleft. PMID:19884665

  16. Tailoring the properties of thermoplastic starch by blending with cinnamyl alcohol and radiation processing: An insight into the competitive grafting and scission reactions

    NASA Astrophysics Data System (ADS)

    Khandal, Dhriti; Mikus, Pierre-Yves; Dole, Patrice; Bliard, Christophe; Soulestin, Jérémie; Lacrampe, Marie-France; Baumberger, Stéphanie; Coqueret, Xavier

    2012-08-01

    The present paper focuses on the effects of electron beam (EB) irradiation on thermoplastic materials based on destructurized starch including glycerol and water as plasticizers to assess the potentiality of cinnamyl alcohol as reactive additive capable of counterbalancing the degradation of the polysaccharide by inducing interchain covalent linkages. The tensile properties at break of test specimens of controlled composition submitted to EB irradiation at doses ranging from 50 to 200 kGy revealed the presence of competitive chain scission and bridging in samples containing cinnamyl alcohol at a relative concentration of 2.5% with regard to dry starch. The occurrence of crosslinking under particular conditions was evidenced by gel fraction measurements. The treatment under radiation was also applied to model blends including maltodextrin as a model for starch and the other ingredients to gain an insight into the radiation induced mechanisms at the molecular level. The presence of cinnamyl alcohol is found to limit degradation. Size exclusion chromatography and gel fraction allowed to monitor the effects and confirmed unambiguously the attachment of UV-absorbing chromophores onto the maltodextrin main chain. The combination of the obtained results demonstrates the possibility of altering in a favorable way the tensile properties of plasticized starch by applying high energy radiation to properly formulated blends including aromatic compounds like cinnamyl alcohol.

  17. Treatment of oil in water emulsions by ceramic-supported polymeric membranes

    SciTech Connect

    Castro, R.P.; Cohen, Y.; Monbouquette, H.G.

    1994-12-31

    A novel membrane was developed by growing polymer chains from the surface of a porous ceramic support, resulting in a composite membrane which combines the mechanical properties of the inorganic membrane with the selective interactions of the polymer. The configuration of the grafted polymer brush layer is determined by solvent-polymer interactions, with a hydrophilic polymer being stretched away from the surface by aqueous solutions and collapsed against the surface by organic solvents. This behavior of the grafted chains provides Ceramic-Supported Polymeric (CSP) membranes with unique properties for certain water treatment applications. One application envisioned for these CSP membranes, in which the selectivity is influenced by interactions between the solvent and the grafted polymer, is the cross-flow filtration of an oil-in-water emulsion. In this case, a hydrophilic grafted Polyvinylpyrrolidone (PVP) brush layer expanded into the pore volume due to the affinity of the polymer for water. These extended grafted chains preferentially allow the passage of water over oil, producing a permeate stream with a lower total organic carbon content compared to an unmodified membrane. Another advantage of the CSP membrane is in reducing permeate flux decline believed to be caused by the adsorption of oil onto the membrane surface. For the PVP-modified CSP membrane, the grafted polymer alters the membrane surface character from hydrophobic to hydrophilic, reducing the tendency for oil adsorption. This phenomenon was demonstrated by comparison of permeate flow rate behavior for both unmodified and graft polymerized (CSP) membranes.

  18. Surface properties and reduced biofouling of graft-copolymers that possess oppositely charged groups.

    PubMed

    Herzberg, Moshe; Sweity, Amer; Brami, Matan; Kaufman, Yair; Freger, Viatcheslav; Oron, Gideon; Belfer, Sophia; Kasher, Roni

    2011-04-11

    Microbial biofilms and their components present a major obstacle for ensuring the long-term effectiveness of membrane processes. Graft polymerization on membrane surfaces, in general, and grafting with oppositely charged monomers, have been shown to reduce biofouling significantly. In this study, surface forces and macromolecular properties of graft copolymers that possess oppositely charged groups were related to their potent antibiofouling behavior. Graft polymerization was performed using the negatively charged 3-sulphopropyl methacrylate (SPM) and positively charged [2-(methacryloyloxy)ethyl]-trimethylammonium (MOETMA) monomers to yield a copolymer layer on polyvinylidene fluoride (PVDF) surface. Quartz crystal microbalance with dissipation monitoring (QCM-D) technology was used to monitor the reduced adsorption of extracellular polymeric substances (EPS) extracted from a membrane bioreactor (MBR) wastewater treatment facility. Complemented measurements of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy provided evaluation of the antifouling properties of the surface. Increase in water content in grafted layer exposed to 100 mM aqueous NaCl solution was observed by QCM-D. Therefore, the grafted copolymer layer is swelled in the presence of 100 mM NaCl because of reversing of polymer self-association by counterions. Force measurements by atomic force microscopy (AFM) showed an increased repulsion between a carboxylate-modified latex (CML) particle probe and a modified PVDF surface, especially in the presence of 100 mM NaCl. The hydration and swelling of the grafted polymer layer are shown to repel EPS and reduce their adsorption. Delineating the surface properties of antifouling grafted layers may lead to the design of novel antifouling surfaces. PMID:21361342

  19. Vascular graft infections.

    PubMed

    Young, Michael H; Upchurch, Gilbert R; Malani, Preeti N

    2012-03-01

    Prosthetic vascular grafting is a commonly performed procedure that is central to the management of arterial disease and renal failure. Though rare, vascular graft infections (VGI) are potentially devastating, and carry a high rate of mortality and amputation. Despite extensive research and clinical experience, VGI remain a daunting therapeutic challenge for surgeons and infectious disease specialists. This article reviews the pathogenesis of VGI, in particular the role of biofilms, as well as the current state of clinical management including diagnostic modalities, surgical options for treatment, antimicrobial therapy, and preventive measures. PMID:22284375

  20. Grafting thermosensitive PNIPAM onto the surface of carbon spheres

    NASA Astrophysics Data System (ADS)

    Guo, Xingmei; Du, Zefeng; Song, Maoning; Qiu, Li; Shen, Yinghua; Yang, Yongzhen; Liu, Xuguang

    2014-12-01

    Thermosensitive polymer poly(N-isopropylacrylamine) (PNIPAM) grafted-carbon spheres (CSs) composites were synthesized and investigate the influence of synthesis parameters on phase transition temperature in order to produce thermosensitive composites with different phase transition temperatures, which may be applied to different application fields. First, vinyl groups were introduced onto the surface of CSs by mixed acid oxidation and reacting with 3-methacryloxypropyl trimethoxysilane. Then, PNIPAM was grafted onto the surface of CSs by surface free-radical polymerization. According to the differential scanning calorimetric analysis, the PNIPAM-grafted CSs composites are temperature responsive. The weight ratio of monomer to CSs and the initiator dosage had great influence on the polymer shell thickness and the lower critical solution temperature (LCST) of the composites determined by the number of grafted polymer chain, chain length and the cross-link degree. The polymer shell thickness and the LCST of the composites increased with the increase of the amount of monomer in proper range, however, first increase and then decrease with the increasing initiator dosage. The cross-linking agent content affects critically the cross-link degree, and then the LCST. Therefore, the LCST of the PNIPAM-grafted CSs composites was adjustable by changing the synthesis parameters, which lays the basis for CSs application in different fields.

  1. Impact of reaction conditions on architecture and rheological properties of starch graft polyacrylamide polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We carried out experiments examining the impact that solvent selection and reaction conditions have on the radical initiated graft polymerization reaction of acrylamide onto starch. We have also evaluated the rheological properties the starch graftpolyacrylamide product when a gel is formed in water...

  2. Bone Grafts in Craniofacial Surgery

    PubMed Central

    Elsalanty, Mohammed E.; Genecov, David G.

    2009-01-01

    Reconstruction of cranial and maxillofacial defects is a challenging task. The standard reconstruction method has been bone grafting. In this review, we shall describe the biological principles of bone graft healing, as pertinent to craniofacial reconstruction. Different types and sources of bone grafts will be discussed, as well as new methods of bone defect reconstruction. PMID:22110806

  3. Grafting effects on vegetable quality

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In the United States, vegetable grafting is rare and few experiments have been done to determine optimal grafting procedures and production practices for different geographical and climatic regions in America. Grafting vegetables to control soilborne disease is a common practice in Asia, parts of E...

  4. Tunable Pickering emulsions with polymer-grafted lignin nanoparticles (PGLNs).

    PubMed

    Silmore, Kevin S; Gupta, Chetali; Washburn, Newell R

    2016-03-15

    Lignin is an abundant biopolymer that has native interfacial functions but aggregates strongly in aqueous media. Polyacrylamide was grafted onto kraft lignin nanoparticles using reversible addition-fragmentation chain transfer (RAFT) chemistry to form polymer-grafted lignin nanoparticles (PGLNs) that tune aggregation strength while retaining interfacial activities in forming Pickering emulsions. Polymer graft density on the particle surface, ionic strength, and initial water and cyclohexane volume fractions were varied and found to have profound effects on emulsion characteristics, including emulsion volume fraction, droplet size, and particle interfacial concentration that were attributed to changes in lignin aggregation and hydrophobic interactions. In particular, salt concentration was found to have a significant effect on aggregation, zeta potential, and interfacial tension, which was attributed to changes in solubility of both the kraft lignin and the polyacrylamide grafts. Dynamic light scattering, UV-vis spectroscopy, optical microscopy, and tensiometry were used to quantify emulsion properties and nanoparticle behavior. Under all conditions, the emulsions exhibited relatively fast creaming but were stable against coalescence and Ostwald ripening for a period of months. All emulsions were also oil-in-water (o/w) emulsions, as predicted by the Bancroft rule, and no catastrophic phase inversions were observed for any nanoparticle compositions. We conclude that lower grafting density of polyacrylamide on a lignin core resulted in high levels of interfacial activity, as characterized by higher concentration at the water-cyclohexane interface with a corresponding decrease in interfacial tension. These results indicate that the interfacial properties of polymer-grafted lignin nanoparticles are primarily due to the native hydrophobic interactions of the lignin core. These results suggest that the forces that drive aggregation are also correlated with interfacial activities, and polymer-nanoparticle interactions are critical for optimizing interfacial activities. Controlled radical polymerization is a powerful tool for polymer grafting that can leverage the intrinsic interfacial functions of lignin for the formation of Pickering emulsions. PMID:26707776

  5. Nanoconfinement Effect on Polymerization

    NASA Astrophysics Data System (ADS)

    Vaddey, Maitri; Simon, Sindee

    2011-03-01

    Ring-opening metathesis polymerization of endo-dicyclopentadidene (DCPD) with second generation Grubbs catalyst is carried out under nanoscale constraint. Differential scanning calorimetry is used to study the polymerization reaction both in the bulk and in the nanopores of controlled pore glass as a function of heating rate; the Tg of the resulting reaction product is also determined. In 110 nm-diameter pores, DCPD undergoes incomplete polymerization followed by the reverse Diels-Alder reaction to form pentadiene. Decreasing the heating rate shifts both reactions towards lower temperatures but does not avert the side reaction. In the bulk unconfined case, the reverse Diels-Alder reaction only occurs in the absence of catalyst. The glass transition temperature of the nanoconfined polymerization product is 164 °C, approximately 20 °C higher than the polymer prepared under bulk conditions. Reaction kinetics in bulk and nanoconfined cases will also be discussed.

  6. Space environmental effects on polymeric materials

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard L.; Orwoll, Robert A.

    1988-01-01

    Two of the major environmental hazards in the Geosynchronous Earth Orbit (GEO) are energetic charged particles and ultraviolet radiation. The charged particles, electrons and protons, range in energy from 0.1 to 4 MeV and each have a flux of 10 to the 8th sq cm/sec. Over a 30 year lifetime, materials in the GEO will have an absorbed dose from this radiation of 10 to the 10th rads. The ultraviolet radiation comes uninhibited from the sun with an irradiance of 1.4 kw/sq m. Radiation is known to initiate chain sission and crosslinking in polymeric materials, both of which affect their structural properties. The 30-year dose level from the combined radiation in the GEO exceeds the threshold for measurable damage in most polymer systems studied. Of further concern is possible synergistic effects from the simultaneous irradiation with charged particles and ultraviolet radiation. Most studies on radiation effects on polymeric materials use either electrons or ultraviolet radiation alone, or in a sequential combination.

  7. Acrylonitrile grafted to PVDF

    SciTech Connect

    Yang, Jin; Eitouni, Hany Basam

    2015-03-31

    PVDF-g-PAN has been synthesized by grafting polyacrylonitrile onto polyvinylidene fluoride using an ATRP/AGET method. The novel polymer is ionically conducive and has much more flexibility than PVDF alone, making it especially useful either as a binder in battery cell electrodes or as a polymer electrolyte in a battery cell.

  8. Grafting for disease resistance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The primary purpose of grafting vegetables worldwide has been to provide resistance to soilborne diseases. The potential loss of methyl bromide as a soil fumigant combined with pathogen resistance to commonly used pesticides will make resistance to soil born pathogens even more important in the futu...

  9. Grafting for disease resistance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The primary purpose of grafting vegetables worldwide has been to provide resistance to soil-borne diseases. The potential loss of methyl bromide as a soil fumigant combined with pathogen resistance to commonly used pesticides will make resistance to soil-borne pathogens even more important in the fu...

  10. Radical-Mediated Enzymatic Polymerizations.

    PubMed

    Zavada, Scott R; Battsengel, Tsatsral; Scott, Timothy F

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes-catalytic proteins-owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol-ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  11. Radical-Mediated Enzymatic Polymerizations

    PubMed Central

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  12. Accompanying of parameters of color, gloss and hardness on polymeric films coated with pigmented inks cured by different radiation doses of ultraviolet light

    NASA Astrophysics Data System (ADS)

    Bardi, Marcelo Augusto Gonçalves; Machado, Luci Diva Brocardo

    2012-09-01

    In the search for alternatives to traditional paint systems solvent-based, the curing process of polymer coatings by ultraviolet light (UV) has been widely studied and discussed, especially because of their high content of solids and null emission of VOC. In UV-curing technology, organic solvents are replaced by reactive diluents, such as monomers. This paper aims to investigate variations on color, gloss and hardness of print inks cured by different UV radiation doses. The ratio pigment/clear coating was kept constant. The clear coating presented higher average values for König hardness than pigmented ones, indicating that UV-light absorption has been reduced by the presence of pigments. Besides, they have indicated a slight variation in function of cure degree for the studied radiation doses range. The gloss loss related to UV light exposition allows inferring that some degradation occurred at the surface of print ink films.

  13. Development of grafted xyloglucan micelles for pulmonary delivery of curcumin: In vitro and in vivo studies.

    PubMed

    Mahajan, Hitendra S; Mahajan, Prashant R

    2016-01-01

    A novel grafted copolymer consisting of l-lactide grafted xyloglucan was synthesized by polymerization reaction and characterized. The grafted copolymers were analyzed by Fourier-transform infrared spectrometry (FTIR) and (1)H nuclear magnetic resonance ((1)H NMR) was performed to confirm the grafting of l-poly lactic acid on xyloglucan. The grafted polymer forms micelles at the critical micelle concentration of 0.0150 wt% with the average particle size of 102 nm, as determined by particle size analyzer. The zeta potential of the curcumin loaded micelles was -18.2 mV, an acceptable drug loading efficiency of 68.9 ± 0.02% and the entrapment efficiency of 96.38 ± 0.2%. The release study for 5h showed a sustained release property. In vitro assessment demonstrates suitability of micelles as dry powder for inhalation. In vivo studies showed significant improvement in bioavailability on pulmonary administration of curcumin micelles as DPI formulation. The potential for pulmonary delivery curcumin loaded in micelles was evaluated. In conclusion, polymeric micelle based on a newly synthesized grafted xyloglucan could be suitable carrier for pulmonary delivery of curcumin. PMID:26432365

  14. Theoretical study on tethered polymers with explicit grafting points in Θ-solvent

    NASA Astrophysics Data System (ADS)

    Suo, Tongchuan; Yan, Dadong

    2011-02-01

    Systematic studies on the polymers chemically grafted onto a solid substrate with various grafting densities are presented based on the self-consistent mean-field theory (SCMFT). The distribution of the grafting points is explicitly included and all the three coordinates of each grafting point are fixed during the calculations. The existence of solvent molecules is also explicitly considered in the model and the case of Θ-solvent is investigated. The structure of the system is derived by solving the SCMFT equations in three-dimensional space. For the cases of low grafting density, the system is highly inhomogeneous and typical mushroom-like structures are derived. On the other hand, when the grafting density is high enough, the system is nearly homogeneous along the substrate and the polymer concentration profile is consistent with the numerical results of one dimensional SCMFT calculations. The crossover between "mushroom" regime and polymer brush is obtained by tuning the grafting density. In addition, in brush limit, while the root-mean-squared thickness of the brush is linearly dependent on the degree of polymerization, its dependency on the grafting density is in general more complicated than a simple power law.

  15. Mixing in polymeric microfluidic devices.

    SciTech Connect

    Schunk, Peter Randall; Sun, Amy Cha-Tien; Davis, Robert H.; Brotherton, Christopher M. (University of Colorado at Boulder, Boulder, CO)

    2006-04-01

    This SAND report describes progress made during a Sandia National Laboratories sponsored graduate fellowship. The fellowship was funded through an LDRD proposal. The goal of this project is development and characterization of mixing strategies for polymeric microfluidic devices. The mixing strategies under investigation include electroosmotic flow focusing, hydrodynamic focusing, physical constrictions and porous polymer monoliths. For electroosmotic flow focusing, simulations were performed to determine the effect of electroosmotic flow in a microchannel with heterogeneous surface potential. The heterogeneous surface potential caused recirculations to form within the microchannel. These recirculations could then be used to restrict two mixing streams and reduce the characteristic diffusion length. Maximum mixing occurred when the ratio of the mixing region surface potential to the average channel surface potential was made large in magnitude and negative in sign, and when the ratio of the characteristic convection time to the characteristic diffusion time was minimized. Based on these results, experiments were performed to evaluate the manipulation of surface potential using living-radical photopolymerization. The material chosen to manipulate typically exhibits a negative surface potential. Using living-radical surface grafting, a positive surface potential was produced using 2-(Dimethylamino)ethyl methacrylate and a neutral surface was produced using a poly(ethylene glycol) surface graft. Simulations investigating hydrodynamic focusing were also performed. For this technique, mixing is enhanced by using a tertiary fluid stream to constrict the two mixing streams and reduce the characteristic diffusion length. Maximum mixing occurred when the ratio of the tertiary flow stream flow-rate to the mixing streams flow-rate was maximized. Also, like the electroosmotic focusing mixer, mixing was also maximized when the ratio of the characteristic convection time to the characteristic diffusion time was minimized. Physical constrictions were investigated through simulations. The results show that the maximum mixing occurs when the height of the mixing region is minimized. Finally, experiments were performed to determine the effectiveness of using porous polymer monoliths to enhance mixing. The porous polymer monoliths were constructed using a monomer/salt paste. Two salt crystal size ranges were used; 75 to 106 microns and 53 to 180 microns. Mixing in the porous polymer monoliths fabricated with the 75 to 106 micron salt crystal size range was six times higher than a channel without a monolith. Mixing in the monolith fabricated with the 53 to 180 micron salt crystal size range was nine times higher.

  16. Injectable polyHIPEs as high-porosity bone grafts.

    PubMed

    Moglia, Robert S; Holm, Jennifer L; Sears, Nicholas A; Wilson, Caitlin J; Harrison, Dawn M; Cosgriff-Hernandez, Elizabeth

    2011-10-10

    Polymerization of high internal phase emulsions (polyHIPEs) is a relatively new method for the production of high-porosity scaffolds. The tunable architecture of these polyHIPE foams makes them attractive candidates for tissue engineered bone grafts. Previously studied polyHIPE systems require either toxic diluents or high cure temperatures which prohibit their use as an injectable bone graft. In contrast, we have developed an injectable polyHIPE that cures at physiological temperatures to a rigid, high-porosity foam. First, a biodegradable macromer, propylene fumarate dimethacrylate (PFDMA), was synthesized that has appropriate viscosity and hydrophobicity for emulsification. The process of surfactant selection is detailed with particular focus on the key structural features of both polymer (logP values, hydrogen bond acceptor sites) and surfactant (HLB values, hydrogen bond donor sites) that enable stable HIPE formation. Incubation of HIPEs at 37 °C was used to initiate radical cross-linking of the unsaturated double bond of the methacrylate groups to polymerize the continuous phase and lock in the emulsion geometry. The resulting polyHIPEs exhibited ~75% porosity, pore sizes ranging from 4 to 29 μm, and an average compressive modulus and strength of 33 and 5 MPa, respectively. These findings highlight the great potential of these scaffolds as injectable, tissue engineered bone grafts. PMID:21861465

  17. Injectable PolyHIPEs as High Porosity Bone Grafts

    PubMed Central

    Moglia, Robert S.; Holm, Jennifer L.; Sears, Nicholas A.; Wilson, Caitlin J.; Harrison, Dawn M.; Cosgriff-Hernandez, Elizabeth

    2011-01-01

    Polymerization of high internal phase emulsions (polyHIPEs) is a relatively new method for the production of high porosity scaffolds. The tunable architecture of these polyHIPE foams make them attractive candidates for tissue engineered bone grafts. Previously studied polyHIPE systems require either toxic diluents or high cure temperatures which prohibit their use as an injectable bone graft. In contrast, we have developed an injectable polyHIPE that cures at physiological temperatures to a rigid, high-porosity foam. First, a biodegradable macromer, propylene fumarate dimethacrylate (PFDMA), was synthesized that has appropriate viscosity and hydrophobicity for emulsification. The process of surfactant selection is detailed with particular focus on the key structural features of both polymer (log P values, hydrogen bond acceptor sites) and surfactant (HLB values, hydrogen bond donor sites) that enable stable HIPE formation. Incubation of HIPEs at 37°C was used to initiate radical crosslinking of the unsaturated double bond of the methacrylate groups to polymerize the continuous phase and lock in the emulsion geometry. The resulting polyHIPEs exhibited ~75% porosity, pore sizes ranging from 4 to 29 μm, and an average compressive modulus and strength of 33 and 5 MPa, respectively. These findings highlight the great potential of these scaffolds as injectable, tissue engineered bone grafts. PMID:21861465

  18. Siloxane-grafted membranes

    SciTech Connect

    Friesen, Dwayne T.; Obligin, Alan S.

    1989-01-01

    Composite cellulosic semipermeable membranes are disclosed which are the covalently bonded reaction product of an asymmetric cellulosic semipermeable membrane and a polysiloxane containing reactive functional groups. The two reactants chemically bond by ether, ester, amide or acrylate linkages to form a siloxane-grafted cellulosic membrane having superior selectivity and flux stability. Selectivity may be enhanced by wetting the surface with a swelling agent such as water.

  19. Siloxane-grafted membranes

    DOEpatents

    Friesen, D.T.; Obligin, A.S.

    1989-10-31

    Composite cellulosic semipermeable membranes are disclosed which are the covalently bonded reaction product of an asymmetric cellulosic semipermeable membrane and a polysiloxane containing reactive functional group. The two reactants chemically bond by ether, ester, amide or acrylate linkages to form a siloxane-grafted cellulosic membrane having superior selectivity and flux stability. Selectivity may be enhanced by wetting the surface with a swelling agent such as water.

  20. Plasma polymerized high energy density dielectric films for capacitors

    NASA Technical Reports Server (NTRS)

    Yamagishi, F. G.

    1983-01-01

    High energy density polymeric dielectric films were prepared by plasma polymerization of a variety of gaseous monomers. This technique gives thin, reproducible, pinhole free, conformable, adherent, and insoluble coatings and overcomes the processing problems found in the preparation of thin films with bulk polymers. Thus, devices are prepared completely in a vacuum environment. The plasma polymerized films prepared all showed dielectric strengths of greater than 1000 kV/cm and in some cases values of greater than 4000 kV/cm were observed. The dielectric loss of all films was generally less than 1% at frequencies below 10 kHz, but this value increased at higher frequencies. All films were self healing. The dielectric strength was a function of the polymerization technique, whereas the dielectric constant varied with the structure of the starting material. Because of the thin films used (thickness in the submicron range) surface smoothness of the metal electrodes was found to be critical in obtaining high dielectric strengths. High dielectric strength graft copolymers were also prepared. Plasma polymerized ethane was found to be thermally stable up to 150 C in the presence of air and 250 C in the absence of air. No glass transitions were observed for this material.

  1. Preparation and characterization of optical-functional diblock copolymer brushes on hollow sphere surface via atom transfer radical polymerization

    SciTech Connect

    Wang, Li-Ping; Li, Wen-Zhi; Zhao, Li-Min; Zhang, Chun-Juan; Wang, Yan-Dong; Kong, Li-Li; Li, Ling-Ling

    2010-09-15

    The optical-functional poly(methyl methacrylate)-block-Tb complex diblock copolymer brushes grafted from hollow sphere surface via atom transfer radical polymerization were investigated in this work. A sufficient amount of azo initiator was introduced onto hollow sphere surface firstly. Then the monomer methyl methacrylate was polymerized via surface-initiated reverse atom transfer radical polymerization using azo group modified hollow sphere as initiator. Following, the poly(methyl methacrylate) modified hollow sphere was used as maroinitiator for surface-initiated atom transfer radical polymerization of Tb complex. The samples were characterized by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, gel permeation chromatographer and transmission electron microscopy, respectively. The results indicated that the poly(methyl methacrylate) had grafted from hollow sphere surface and the average diameter of hollow core was about 1 {mu}m. The optical properties of the poly(methyl methacrylate)-block-Tb copolymer modified hollow sphere were also reported.

  2. Surface initiated polymerization on pulsed plasma deposited polyallylamine: a polymer substrate-independent strategy to soft surfaces with polymer brushes.

    PubMed

    Yameen, Basit; Khan, Hadayat Ullah; Knoll, Wolfgang; Förch, Renate; Jonas, Ulrich

    2011-11-01

    The deposition of polyallylamine (PAA) adlayers by pulsed plasma polymerization on various types of polymeric substrates has been explored as a general route to amino functionalized polymeric surfaces. These amino groups are highly suitable for anchoring an atom transfer radical polymerization (ATRP) initiator via a robust amide linkage. Subsequent surface initiated ATRP (SI-ATRP) of monomethoxy oligo(ethylene glycol) methacrylate (MeOEGMA) resulted in polyMeOEGMA brush grafted polymer surfaces. This combined strategy of pulsed plasma polymerization with SI-ATRP was demonstrated for five different polymeric substrates namely polyether ether ketone (PEEK), polyethylene terephthalate (PET), polyimide (PI), polypropylene (PP), and polytetrafluoroethylene (PTFE). Analysis of brush layers by attenuated total reflection infrared (ATR-IR) spectroscopy as well as X-ray photoelectron spectroscopy (XPS) fully corroborated the success of the proposed strategy for all substrate types. PMID:21858892

  3. INHIBITING THE POLYMERIZATION OF NUCLEAR COOLANTS

    DOEpatents

    Colichman, E.L.

    1959-10-20

    >The formation of new reactor coolants which contain an additive tbat suppresses polymerization of the primary dissoclation free radical products of the pyrolytic and radiation decomposition of the organic coolants is described. The coolants consist of polyphenyls and condensed ring compounds having from two to about four carbon rings and from 0.1 to 5% of a powdered metal hydride chosen from the group consisting of the group IIA and IVA dispersed in the hydrocarbon.

  4. Molecular Dynamics Simulations of Grafted Layers of Bottle-Brush Polyelectrolytes

    NASA Astrophysics Data System (ADS)

    Russano, Daniel; Carrillo, Jan-Michael; Dobrynin, Andrey

    2011-03-01

    Using molecular dynamics simulations, we study the effect of the brush grafting density and degree of polymerization of the side chains on conformations of brush layers made of charged bottle-brush macromolecules. The thickness of the brush layer first decreases with increasing brush grafting density; then, it saturates and remains constant in the wide interval of the brush grafting densities. The brush layers consisting of the bottle-brush macromolecules with longer side chains have a larger layer thickness. The elongation of the side chains of the bottle-brush macromolecules decreases with increasing brush grafting density. This contraction of the side chains is due to counterion condensation inside the volume occupied by bottle-brushes. Our simulations showed that counterion condensation is a multiscale process reflecting different symmetries of the bottle-brush layer. NSF: DMR-1004576.

  5. Blood compatibility of AAc, HEMA, and PEGMA-grafted cellulose film

    NASA Astrophysics Data System (ADS)

    Nho, Young Chang; Kwon, Oh Hyun

    2003-03-01

    To improve surface blood compatibility on cellulose film for hemodialysis, acrylic acid, 2-hydroxyethyl methacrylate and three kinds of polyethylene glycol methacrylates were grafted onto the cellulose film surface by radiation grafting technique. Heparin was introduced onto the grafted cellulose film surfaces. The grafting and heparinization were confirmed by Fourier transform infrared spectroscopy in the attenuated total reflectance mode and electron spectroscopy for chemical analysis. The blood compatibility of the modified cellulose film was examined by the determination of platelet adhesion and thrombus formation.

  6. Copolymer Synthesis and Characterization by Post-Polymerization Modification

    NASA Astrophysics Data System (ADS)

    Galvin, Casey James

    This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in developing technologies that use SGPAs in aqueous environments, and point to a need for potential alternative grafting chemistries. The behavior of SGPAs in vapor environments remains an underexplored phenomenon. By changing systematically the chemistry of SGPAs derived from a parent sample, the influence of side chain functional groups on the swelling of weak and strong polyelectrolyte brushes in the presence of water, methanol and ethanol vapors is explored. The extent of swelling and solvent uptake depends strongly on the chemistry in the polymer side chain and of the solvent. Despite bearing a permanent electrostatic charge in the side chain, the strong polyelectrolyte brushes exhibit no behavior typical of polyelectrolytes in water due to no dissociation of the counterion. Of particular interest is the behavior in humid environments of an SGPA bearing a zwitterionic group in its side chain, which results in exposure of electrostatic charges without counterions. Using substrates bearing the aforementioned sigma gradient of polymeric grafts, evidence of inter- and intramolecular complex formation is presented. Finally, a method of developing SGPAs by polymerizing bulk polymer chains through surface-grafted monomers (SGMs) is described. The SGMs are incorporated onto a solid substrate using the same PPM reaction employed in the degrafting and vapor swelling experiments, highlighting the versatility of PPM. The thickness of these SGPAs is correlated to the bulk polymer chains MW, suggesting this technique can be used in existing industrial bulk polymerization processes.

  7. [Grafts in esthetic and functional corrective rhinoplasty].

    PubMed

    Cannoni, M; Pech, A; Waller, P Y; Zanaret, M

    1988-01-01

    Results of the use of grafts in primary and secondary rhinoplasty are reported, the grafts being either of cartilage (concha auriculae, nasal septum, alar cartilage), bone (mastoid, ilium) or connective tissue (temporal aponeurosis). The distinction is made between modelling grafts of softened cartilage, supporting grafts of non-softened cartilage and mastoid bone, of bone reconstruction and of cartilaginous filling grafts. PMID:3064668

  8. Thermally and photoinduced polymerization of ultrathin sexithiophene films

    SciTech Connect

    Sander, Anke; Hammer, Rene; Duncker, Klaus; Förster, Stefan; Widdra, Wolf

    2014-09-14

    The thermally-induced polymerization of α-sexithiophene (6T) molecules on Ag(001) and Au(001) gives rise to long unbranched polymer chains or branched polymer networks depending on the annealing parameters. There, the onset temperature for polymerization depends on the strength of interaction with the underlying substrate. Similar polymerization processes are also induced by ultraviolet radiation with photon energies between 3.0 and 4.2 eV. Radical formation by an electronic excitation in the 6T molecule is proposed as the driving mechanism that necessitates the interplay with the metallic substrate.

  9. Elastic Energy Driven Polymerization

    PubMed Central

    Wang, Andrew; Zocchi, Giovanni

    2009-01-01

    We present a molecular system where polymerization is controlled externally by tuning the elastic energy of the monomers. The elastic energy, provided by a DNA molecular spring, destabilizes the monomer state through a process analogous to domain swapping. This energy can be large (of ∼10 kT) and thus drive polymerization at relatively low monomer concentrations. The monomer-dimer equilibrium provides a measurement of the elastic energy of the monomer, which in this construction appears limited by kink formation in the DNA molecular spring, in accord with previous theoretical and experimental investigations of the elasticity of sharply bent DNA. PMID:19289060

  10. Dead Sea Minerals loaded polymeric nanoparticles.

    PubMed

    Dessy, Alberto; Kubowicz, Stephan; Alderighi, Michele; Bartoli, Cristina; Piras, Anna Maria; Schmid, Ruth; Chiellini, Federica

    2011-10-15

    Therapeutic properties of Dead Sea Water (DSW) in the treatment of skin diseases such as atopic dermatitis, psoriasis and photo aging UV damaged skin have been well established. DSW is in fact rich in minerals such as calcium, magnesium, sodium, potassium, zinc and strontium which are known to exploit anti-inflammatory effects and to promote skin barrier recovery. In order to develop a Dead Sea Minerals (DSM) based drug delivery system for topical therapy of skin diseases, polymeric nanoparticles based on Poly (maleic anhydride-alt-butyl vinyl ether) 5% grafted with monomethoxy poly(ethyleneglycol) 2000 MW (PEG) and 95% grafted with 2-methoxyethanol (VAM41-PEG) loaded with DSM were prepared by means of a combined miniemulsion/solvent evaporation process. The resulting nanoparticles were characterized in terms of dimension, morphology, biocompatibility, salt content and release. Cytocompatible spherical nanoparticles possessing an average diameter of about 300 nm, a time controlled drug release profile and a high formulation yield were obtained. PMID:21676600

  11. Surface Grafted Polysarcosine as a Peptoid Antifouling Polymer Brush

    PubMed Central

    Lau, King Hang Aaron; Ren, Chunlai; Sileika, Tadas S.; Park, Sung Hyun; Szleifer, Igal; Messersmith, Phillip B.

    2012-01-01

    Poly(N-substituted glycine) “peptoids” are a class of peptidomimetic molecules receiving significant interest as engineered biomolecules. Sarcosine (i.e. poly(N-methyl glycine)) has the simplest sidechain chemical structure of this family. In this contribution, we demonstrate that surface-grafted polysarcosine (PSAR) brushes exhibit excellent resistance to non-specific protein adsorption and cell attachment. Polysarcosine was coupled to a mussel adhesive protein inspired DOPA-Lys pentapeptide, which enabled solution grafting and control of the surface chain density of the PSAR brushes. Protein adsorption was found to decrease monotonically with increasing grafted chain densities, and protein adsorption could be completely inhibited above certain critical chain densities specific to different polysarcosine chain-lengths. The dependence of protein adsorption on chain length and density was also investigated by a molecular theory. PSAR brushes at high chain length and density were shown to resist fibroblast cell attachment over a 7 wk period, as well as resist the attachment of some clinically relevant bacteria strains. The excellent antifouling performance of PSAR may be related to the highly hydrophilic character of polysarcosine, which was evident from high-pressure liquid chromatography measurements of polysarcosine and water contact angle measurements of the PSAR brushes. Peptoids have been shown to resist proteolytic degradation and polysarcosine could be produced in large quantities by N-carboxy anhydride polymerization. In summary, surface grafted polysarcosine peptoid brushes hold great promise for antifouling applications. PMID:23101930

  12. PNIPAM grafting on the surface of zirconium phosphate

    NASA Astrophysics Data System (ADS)

    Li, Hai; Wang, Xuezhen; Cheng, Zhengdong; Cheng's Group Team, Dr.

    2015-03-01

    We are reporting for the first time the grafting of the thermoresponsive polymer PNIPAM (poly n-isoproprylacrylamide) on the surface of inorganic nanoplates zirconium phosphate. Particularly, the grafting on inorganic nanoplates using gamma rays has never scarcely been reported and yet proved to be successful in our synthesis. We proved that by gamma ray irradiation, the peroxide groups has been produced on the ZrP particles since that peroxide groups, on the surface of the hexagonal nanoplates, which upon heating initiated the free radical polymerization and subsequent attachment of PNIPAM. The presence of covalent band between ZrP and PNIPAM were observed and characterized by TGA, FTIR and solid state NMR respectively. The attachment of a thermoresponsive polymer to ZrP nanocrystals brings thus remarkable possibilities for their employment in the fields of medicine, oil industry, as well as physics.

  13. [The saphenous vein graft diseases].

    PubMed

    Yavuz, Turhan; Kutsal, Ali

    2002-03-01

    Graft occlusions are the main problems that may arise during long-term follow-up period after coronary artery bypass surgery. Knowledge of pathologies developed in saphenous grafts and attempts to reduce their frequency are important for reduction of the incidence of saphenous graft vein occlusions. For today the patency rate for 10 years saphenous vein grafts are about 60%. Along with intraoperative technical factors, there are a lot of factors contributed to the development occlusion during long-term follow-up period. In this review we aimed to analyze the factors affecting saphenous vein pathologies and propose preventive measures. PMID:12101795

  14. Studies in reactive extrusion processing of biodegradable polymeric materials

    NASA Astrophysics Data System (ADS)

    Balakrishnan, Sunder

    Various reaction chemistries such as Polymerization, Polymer cross-linking and Reactive grafting were investigated in twin-screw extruders. Poly (1,4-dioxan-2-one) (PPDX) was manufactured in melt by the continuous polymerization of 1,4-dioxan-2-one (PDX) monomer in a twin-screw extruder using Aluminum tri-sec butoxide (ATSB) initiator. Good and accurate control over molecular weight was obtained by controlling the ratio of monomer to initiator. A screw configuration consisting of only conveying elements was used for the polymerization. The polymerization reaction was characterized by a monomer-polymer dynamic equilibrium, above the melting temperature of the polymer, limiting the equilibrium conversion to 78-percent. Near complete (˜100-percent) conversion was obtained on co-polymerizing PDX monomer with a few mol-percent (around 8-percent) Caprolactone (CL) monomer in a twin-screw extruder using ATSB initiator. The co-polymers exhibited improved thermal stability with reduction in glass transition temperature. The extruder was modeled as an Axial Dispersed Plug Flow Reactor for the polymerization of CL monomer using Residence Time Distribution (RTD) Analysis. The model provided a good fit to the experimental RTD and conversion data. Aliphatic and aliphatic-aromatic co-polyesters, namely Polycaprolactone (PCL) and Poly butylenes (adipate-co-terephthalate) (Ecoflex) were cross-linked in a twin-screw extruder using radical initiator to form micro-gel reinforced biodegradable polyesters. Cross-linked Ecoflex was further extrusion blended with talc to form blends suitable to be blown into films. A screw configuration consisting of conveying and kneading elements was found to be effective in dispersion of the talc particles (5--10 microns) in the polyester matrix. While the rates of crystallization increased for the talc filled polyester blends, overall crystallinity reduced. Mechanical, tear and puncture properties of films made using the talc filled polyester blends were comparable to linear low density Polyethylene (LDPE). Ecoflex-Thermoplastic Starch (TPS) graft co-polymers were continuously manufactured in melt with maleic acid catalyst using a twin-screw co-rotating extruder. The graft co-polymer was completely extractable in Dichloromethane and formed transparent films on solvent casting. Regular corn-starch was maleated in a twin-screw extruder using maleic anhydride or maleic acid, glycerol plasticizer and optional radical initiator. Confirmation of reactivity of maleic acid onto the starch backbone was confirmed by Fourier Transformed Infra Red (FTIR) Spectroscopy. (Abstract shortened by UMI.)

  15. Grafting glycidyl methacrylate to Sepharose gel for fabricating high-capacity protein anion exchangers.

    PubMed

    Wang, Qianqian; Yu, Linling; Sun, Yan

    2016-04-22

    To develop ion exchangers of high protein adsorption capacity, we have herein introduced atom transfer radical polymerization (ATRP) method to graft glycidyl methacrylate (GMA) onto Sepharose FF gel. GMA-grafted Sepharose FF resins of four grafting densities and different grafting chain lengths were obtained by adjusting reaction conditions. The epoxy groups on the grafted chains were functionalized by modification with diethylamine (DEA), leading to the fabrication of Sepharose-based anion exchangers of 14 different grafting densities and/or grafting chain lengths. The resins were first characterized for the effects of grafting density, chain length and ionic strength on pore sizes by inverse size exclusion chromatography. Then, the resins were evaluated by adsorption equilibria of bovine serum albumin (BSA) as a function of ionic capacity (IC) (chain length) at individual grafting densities. It was observed that at each grafting density there was a specific IC value (chain length) that offered the maximum equilibrium capacity. Of the resins with maximum values at individual grafting densities, the resin of the second grafting density with an IC value of 330mmol/L (denoted as FF-Br2-pG-D330) showed the highest capacity, 264mg/mL, about two times higher than that of the traditional ungrafted resin Q Sepharose FF (137mg/mL). This resin also showed the most favorable uptake kinetics among the resins of similar IC values but different grafting densities, or of the same grafting density but different IC values. Effects of ionic strength showed that the capacities of FF-Br2-pG-D330 were much higher than Q Sepharose FF at a wide range of NaCl concentrations (0-200mmol/L), and the uptake rates of the two resins were similar in the ionic strength range. Therefore, the dynamic binding capacity values of BSA on FF-Br2-pG-D330 were much higher than Q Sepharose FF as demonstrated at different residence times and ionic strengths. Taken together, the research has proved the success in the fabrication of high-capacity protein anion exchangers by grafting GMA onto Sepharose gel. PMID:27018187

  16. Ibuprofen microencapsulation within acrylamide-grafted chitosan and methylcellulose interpenetrating polymer network microspheres: Synthesis, characterization, and release studies.

    PubMed

    Bulut, Emine

    2016-06-01

    This study deals with the development of interpenetrating polymer network (IPN) microspheres of acrylamide (AAm) grafted onto a chitosan (CS) backbone and methylcellulose (MC). Chitosan-graft-polyacrylamide (CS-g-PAAm) was synthesized by cerium (IV) ammonium nitrate-induced free radical graft polymerization. The grafting percentage was found to be 50.58%. The synthesized graft copolymer and MC were used to prepare microspheres by the water-in-oil (w/o) emulsion-crosslinking method, and crosslinked with glutaraldehyde (GA) as drug delivery matrices of ibuprofen (IBU). The release of IBU from microspheres decreased when the amount of CS-g-PAAm in the polymer matrix and amount of crosslinker added were increased, while it increased with the increase of the IBU/polymer ratio. PMID:25749277

  17. Variable Effect during Polymerization

    ERIC Educational Resources Information Center

    Lunsford, S. K.

    2005-01-01

    An experiment performing the polymerization of 3-methylthiophene(P-3MT) onto the conditions for the selective electrode to determine the catechol by using cyclic voltammetry was performed. The P-3MT formed under optimized conditions improved electrochemical reversibility, selectivity and reproducibility for the detection of the catechol.

  18. Protein specific polymeric immunomicrospheres

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Dreyer, William J. (Inventor)

    1980-01-01

    Small, round, bio-compatible microspheres capable of covalently bonding proteins and having a uniform diameter below about 3500 A are prepared by substantially instantaneously initiating polymerization of an aqueous emulsion containing no more than 35% total monomer including an acrylic monomer substituted with a covalently bondable group such as hydroxyl, amino or carboxyl and a minor amount of a cross-linking agent.

  19. Poly(2-methacryloyloxyethyl phosphorylcholine) grafting and vitamin E blending for high wear resistance and oxidative stability of orthopedic bearings.

    PubMed

    Kyomoto, Masayuki; Moro, Toru; Yamane, Shihori; Watanabe, Kenichi; Hashimoto, Masami; Takatori, Yoshio; Tanaka, Sakae; Ishihara, Kazuhiko

    2014-08-01

    The ultimate goal in manipulating the surface and substrate of a cross-linked polyethylene (CLPE) liner is to obtain not only high wear resistance but also high oxidative stability and high-mechanical properties for life-long orthopedic bearings. We have demonstrated the fabrication of highly hydrophilic and lubricious poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) grafting layer onto the antioxidant vitamin E-blended CLPE (HD-CLPE(VE)) surface. The PMPC grafting layer with a thickness of 100 nm was successfully fabricated on the vitamin E-blended CLPE surface by using photoinduced-radical graft polymerization. Since PMPC has a highly hydrophilic nature, the water wettability and lubricity of the PMPC-grafted CLPE and HD-CLPE(VE) surfaces were greater than that of the untreated CLPE surface. The PMPC grafting contributed significantly to wear reduction in a hip-joint simulator wear test. Despite high-dose gamma-ray irradiation for cross-linking and further UV irradiation for PMPC grafting, the substrate modified by vitamin E blending maintained high-oxidative stability because vitamin E is an extremely efficient radical scavenger. Furthermore, the mechanical properties of the substrate remained almost unchanged even after PMPC grafting or vitamin E blending, or both PMPC grafting and vitamin E blending. In conclusion, the PMPC-grafted HD-CLPE(VE) provided simultaneously high-wear resistance, oxidative stability, and mechanical properties. PMID:24836953

  20. Radiation effect on poly ( p-sodium styrene sulphonate) of different degrees of polymerization in aqueous solution: pulse radiolysis and steady state study

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Y. K.; Mohan, H.; Sabharwal, S.; Mukherjee, T.

    2001-09-01

    Radiation induced effects on poly ( p-sodium styrene sulphonate) (PSSS) of two molecular weights, namely 10 6 and 70,000 in aqueous solution have been investigated by steady state and pulse radiolysis (PR) techniques. The reactions of primary radicals of water radiolysis such as OH radical, e aq-, H atom, some oxidizing radicals like N 3rad , Cl 2rad - and SO 4rad - and reducing species like CO 2rad - with PSSS have been investigated. The results indicate that the reactivity of these species towards PSSS is a function of molecular weight of PSSS. The absorption spectra of transient species produced when dilute aqueous solutions of PSSS of different molecular weights are subjected to pulse radiolysis have been compared. Rate constants for the reaction of OH radical and H atom with PSSS have been evaluated both by competition kinetics method and by direct observation of build up of transient species. The results indicate that OH radical and H atom react with PSSS in different ways. Near neutral pH, the OH radical reacts with substituted pendant aromatic ring of the PSSS to form an adduct, with a rate constant of 5.5×10 8 and 1.1×10 9 dm 3 mol -1 s -1 for PSSS of molecular weights 10 6 and 70,000, respectively. H atom on the other hand abstracts H atom from the PSSS backbone as well as forms an adduct by reacting with aromatic ring. The rate constant values for reaction of aqueous electron with PSSS were found to be 5×10 7 dm 3 mol -1 s -1 ( Mw=10 6) and 2.2×10 8 dm 3 mol -1 s -1 ( Mw=70,000). The anion formed did not transfer electron to methyl viologen in the pH range of 6-10.5. The viscosity of the aqueous PSSS solution decreases with irradiation, up to doses of 1000 kGy indicating degradation of PSSS in this dose range. The PSSS of higher molecular weight is more prone to degradation. The chain scission is a function of dose rate, concentration of polymer and ambient of irradiation. At doses beyond ˜2500 kGy there is a sharp increase in viscosity of the PSSS solutions till the solutions set to a soft, sticky gel mass. The gelation dose ( Dgel) is a function of molecular weight of the polymer and initial polymer concentration. In the presence of crosslinking agent like N, N-methylene bis acrylamide, the gelation was faster for PSSS of higher molecular weight. Gelation was most efficient for 20% (w/w) polymer concentration.

  1. Understanding the grafting of telechelic polymers on a solid substrate to form loops

    SciTech Connect

    Huang, Zhenyu; Ji, Haining; Mays, Jimmy; Dadmun, Mark D

    2008-01-01

    Recent experimental and theoretical studies have demonstrated that relative to singly tethered chains, the presence of polymer loops at interfaces significantly improves interfacial properties such as adhesion, friction, and wettability. In the present study, a simple system was studied to examine the formation of polymeric loops on a solid surface, where the grafting of carboxylic acid terminated telechelic polystyrene from the melt to an epoxy functionalized silicon is chosen. The impact of telechelic molecular weight, grafting temperature, and surface functionality on the telechelic attachment process is studied. It was found that grafting of the telechelic to the surface at both ends to form loops is the primary product of this grafting process. Moreover, examination of the kinetics of the grafting process indicates that it is reaction controlled. Fluorescence tagging of the dangling ends of singly bound chains provides a mechanism to monitor their time evolution during grafting, and these results indicate that the grafting process is accurately described by recent Monte Carlo simulation work. The results also provide a method to control the extent of loop formation at interfaces and therefore provide an opportunity to further understand the role of the loops in the interfacial properties in multicomponent polymer systems.

  2. Synthesis and applications of poly(2-hydroxyethylmethacrylate) grafted agar: a microwave based approach.

    PubMed

    Rani, G Usha; Mishra, Sumit; Pathak, Gopal; Jha, Usha; Sen, Gautam

    2013-10-01

    Synthesis of graft copolymers under the influence of microwave radiation alone is a rapid, efficient, clean, cheap, convenient, energy-saving and green method. Grafting of poly(2-hydroxyethylmethacrylate) on agar backbone was carried out under the influence of microwave radiation. The synthesis is optimized in terms of percentage grafting and intrinsic viscosity, by varying the microwave irradiation time and monomer (2-hydroxyethylmethacrylate) concentration. The synthesized graft copolymers have been characterized by intrinsic viscosity measurement, FTIR spectroscopy, UV-spectroscopy, elemental analysis (C, H, N, & S), thermal studies and scanning electron microscopy (SEM). Flocculation efficacy of the synthesized graft copolymers was studied in 0.25% kaolin and 1% coal fine suspension, through 'jar test' procedure. Further, flocculation efficacy of the best grade, coagulant (alum) and agar were studied for possible application in remediation of metals from river water. PMID:23850679

  3. Molecular architecture requirements for polymer-grafted lignin superplasticizers.

    PubMed

    Gupta, Chetali; Sverdlove, Madeline J; Washburn, Newell R

    2015-04-01

    Superplasticizers are a class of anionic polymer dispersants used to inhibit aggregation in hydraulic cement, lowering the yield stress of cement pastes to improve workability and reduce water requirements. The plant-derived biopolymer lignin is commonly used as a low-cost/low-performance plasticizer, but attempts to improve its effects on cement rheology through copolymerization with synthetic monomers have not led to significant improvements. Here we demonstrate that kraft lignin can form the basis for high-performance superplasticizers in hydraulic cement, but the molecular architecture must be based on a lignin core with a synthetic-polymer corona that can be produced via controlled radical polymerization. Using slump tests of ordinary Portland cement pastes, we show that polyacrylamide-grafted lignin prepared via reversible addition-fragmentation chain transfer polymerization can reduce the yield stress of cement paste to similar levels as a leading commercial polycarboxylate ether superplasticizer at concentrations ten-fold lower, although the lignin material produced via controlled radical polymerization does not appear to reduce the dynamic viscosity of cement paste as effectively as the polycarboxylate superplasticizer, despite having a similar affinity for the individual mineral components of ordinary Portland cement. In contrast, polyacrylamide copolymerized with a methacrylated kraft lignin via conventional free radical polymerization having a similar overall composition did not reduce the yield stress or the viscosity of cement pastes. While further work is required to elucidate the mechanism of this effect, these results indicate that controlling the architecture of polymer-grafted lignin can significantly enhance its performance as a superplasticizer for cement. PMID:25693832

  4. Oriented immobilization of proteins on grafted porous polymers

    NASA Astrophysics Data System (ADS)

    Carbajal, M. Laura; Smolko, Eduardo E.; Grasselli, Mariano

    2003-08-01

    The modification of polymers by radiation grafting has been utilized for several decades. The penetrability of gamma rays allows to modify the internal surfaces of porous materials retaining its mechanical properties. In recent years applications of these materials to obtain chromatographic supports and biocatalysts have been reported. In this work, we described the grafting of glycidyl methacrylate (GMA) onto a macroporous polysulfone polymer. Reproducible amount of grafting, from 10% to 60% was obtained by choosing favourable monomer concentration and gamma radiation doses from 6 kGy up. Afterwards, iminodiacetic acid (IDA) and amino phenyl arsine oxide (PAO) were covalently attached to the grafted polyGMA, in correspondence with the grafting degree. Later on, a recombinant histidin-patch thioredoxin protein (HP-rTrx) was immobilized onto this surface by two different ways, involving specific protein orientations. The first one involves an IDA-Ni 2+ complex and three HP-rTrx's histidines and the other one involves a co-ordination site between PAO and two proximal HP-rTrx's cysteines, which corresponds to the active site of the enzyme. Specific polyclonal antibodies recognize HP-rTrx on the polymer. Proper orientation of the protein was confirmed by HP-rTrx activity measurements. The described procedure allows the successful oriented immobilization of a protein onto a macroporous polysulfone material.

  5. Preparation of an Antibacterial Poly(ionic liquid) Graft Copolymer of Hydroxyethyl Cellulose.

    PubMed

    Joubert, Fanny; Yeo, R Paul; Sharples, Gary J; Musa, Osama M; Hodgson, David R W; Cameron, Neil R

    2015-12-14

    Poly(ionic liquid)s (P(IL)s) of different degrees of polymerization (10, 50, and 100) were prepared via RAFT polymerization using an alkyne-terminated xanthate as transfer agent, with a monomer conversion of up to ∼80% and a ĐM of 1.5 for P(IL)100. Subsequently, P(IL) chains were coupled to (15)N-labeled azido-functionalized hydroxyethyl cellulose (HEC), forming graft copolymers of HEC with different chain length and graft densities, which were characterized using ((13)C and (15)N) CP-MAS NMR and FT-IR spectroscopies. The antibacterial activities of HEC-g-P(IL)s were tested against Escherichia coli and Staphylococcus aureus and were comparable to ampicillin, a well-known antibiotic, demonstrating efficient activity of the graft copolymers against bacteria. Moreover, HEC-g-P(IL)s were slightly more effective against E. coli than S. aureus. A decrease in graft density of P(IL)10 on the HEC backbone decreased the activity of the graft copolymers against both bacteria. These findings suggest that HEC-g-P(IL) could find applications as an antiseptic compound, for example, in paint formulation. PMID:26544047

  6. Enzymatic Hydrophobic Modification of Jute Fibers via Grafting to Reinforce Composites.

    PubMed

    Liu, Ruirui; Dong, Aixue; Fan, Xuerong; Yu, Yuanyuan; Yuan, Jiugang; Wang, Ping; Wang, Qiang; Cavaco-Paulo, Artur

    2016-04-01

    Horseradish peroxidase (HRP)/H2O2 system catalyzes the free-radical polymerization of aromatic compounds such as lignins and gallate esters. In this work, dodecyl gallate (DG) was grafted onto the surfaces of lignin-rich jute fabrics by HRP-mediated oxidative polymerization with an aim to enhance the hydrophobicity of the fibers. The DG-grafted jute fibers and reaction products of their model compounds were characterized by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results clearly indicated the grafting of DG to the jute fiber by HRP. Furthermore, the hydrophobicity of jute fabrics was determined by measuring the wetting time and static contact angle. Compared to the control sample, the wetting time and static contact angle of the grated fabrics changed from ~1 s to 1 h and from ~0° to 123.68°, respectively. This clearly proved that the hydrophobicity of jute fabrics improved considerably. Conditions of the HRP-catalyzed DG-grafting reactions were optimized in terms of the DG content of modified jute fabrics. Moreover, the results of breaking strength and elongation of DG-grafted jute/polypropylene (PP) composites demonstrated improved reinforcement of the composite due to enzymatic hydrophobic modification of jute fibers. PMID:26754422

  7. The study of UHMWPEF surface modification with plasma- induced polymerization

    NASA Astrophysics Data System (ADS)

    Zhang, Yu-Fang; Jia, Qing-Xiu; Wang, Xin; Zhang, Pei-Ran

    2015-07-01

    In order to improve the surface activity levels of the ultrahigh molecular weight polyethylene fiber (UHMWPEF), as well as enhancing the interface strength of the UHMWPEF based composite materials, the method of plasma-induced polymerization was applied to modify the UHMWPEF surface. In this study, the plasma's power, time, pressure and the grafting monomer concentration were introduced. Also, through a well-conducted comparison and analysis of the grafting rate, fabric surface functional groups and the microcosmic morphology, the most suitable plasma modification process was discovered and determined. The mechanics performance of hybrid composites with the modified UHMWPEF and unidirectional carbon fiber cloth (CF) was tested to reveal that, compared with the unmodified composites, the tensile strength and the laminar shear strength could be improved.

  8. RAFT-synthesized Graft Copolymers that Enhance pH-dependent Membrane Destabilization and Protein Circulation Times

    PubMed Central

    Crownover, Emily; Duvall, Craig L.; Convertine, Anthony; Hoffman, Allan S.; Stayton, Patrick S.

    2012-01-01

    Here we describe a new graft copolymer architecture of poly(propylacrylic acid) (polyPAA) that displays potent pH-dependent, membrane-destabilizing activity and in addition is shown to enhance protein blood circulation kinetics. PolyPAA containing a single telechelic alkyne functionality was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization with an alkyne-functional chain transfer agent (CTA) and coupled to RAFT polymerized poly(azidopropyl methacrylate) (polyAPMA) through azide-alkyne [3+2] Huisgen cycloaddition. The graft copolymers become membrane destabilizing at endosomal pH values and are active at significantly lower concentrations than the linear polyPAA. A biotin terminated polyPAA graft copolymer was prepared by grafting PAA onto polyAPMA polymerized with a biotin functional RAFT CTA. The blood circulation time and biodistribution of tritium labeled avidin conjugated to the polyPAA graft copolymer was characterized along with a clinically utilized 40 kDa branched polyethylene glycol (PEG) also possessing biotin functionalization. The linear and graft polyPAA increase the area under the curve (AUC) over avidin alone by 9 and 12 times, respectively. Furthermore, polyPAA graft copolymer conjugates accumulated in tumor tissue significantly more than the linear polyPAA and the branched PEG conjugates. The collective data presented in this report indicate that the polyPAA graft copolymers exhibit robust pH-dependent, membrane-destabilizing activity, low cytotoxicity and significantly enhance blood circulation time and tumor accumulation. PMID:21699931

  9. Grafting effects on vegetable quality

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vegetable grafting began in the 1920s to control soil-borne disease. It is now a common practice in Asia, parts of Europe, and the Middle East. In Japan and Korea most of the cucurbits and tomatoes (Lycopersicon esculentum Mill.) grown are grafted. This practice is rare in the U.S. and there have...

  10. Polyether/Polyester Graft Copolymers

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

    1986-01-01

    Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

  11. Listeria monocytogenes Endovascular Graft Infection

    PubMed Central

    Heysell, Scott K.; Hughes, Molly A.

    2016-01-01

    Although best managed by surgical resection, we present a case of Listeria monocytogenes endovascular graft infection alternatively treated with graft retention and antibiotic induction followed by a lifelong suppressive course. The epidemiological, pathological, and clinical features of this unique entity are reviewed. PMID:26835477

  12. Preparation and application of polymer-grafted magnetic nanoparticles for lipase immobilization

    NASA Astrophysics Data System (ADS)

    Yong, Yang; Bai, Yongxiao; Li, Yanfeng; Lin, Lei; Cui, Yanjun; Xia, Chungu

    Functionalized superparamagnetic particles were prepared by graft polymerization of glycidyl methacrylate and methacryloxyethyl trimethyl ammonium chloride onto the surface of modified-Fe 3O 4 nanoparticles. The resultant particles were characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. The results indicate that the polymer chains had been effectively grafted onto the surface of Fe 3O 4 nanoparticles. The functionalized particles remained dispersive and superparamagnetic. Lipase was immobilized on the magnetic particles under mild conditions by electrostatic adsorption and covalent binding with the activity recovery up to 70.4%. The immobilized lipase had better thermal stability compared to free lipase.

  13. Dynamic testing of bone grafts.

    PubMed

    Plominski, Janusz; Watral, Zbigniew; Kwiatkowski, Krzysztof

    2008-01-01

    The influence of cycling loading force on the substrate made of frozen bone grafts was investigated. Three layers of bone grafts were compacted in a spherical model of hip joint acetabulum and then subjected to a sinusoidal loading force. For each layer a series of N = 30 loading cycles were performed. The least impacted grafts were located in the upper part of the acetabulum, close to its opening, whereas the bed is the most compacted part. Compacting is a non-linear process which quickly loses its dynamics during subsequent cycles. Most of the compacting was observed during the first cycles and the deformation of bone grafts has clearly plastic character. Bone grafts initially compacted by orthopedist undergo further compacting when exposed to a cyclic load. PMID:19385509

  14. Polymeric blends for sensor and actuation dual functionality

    NASA Technical Reports Server (NTRS)

    St. Clair, Terry L. (Inventor); Harrison, Joycelyn S. (Inventor); Su, Ji (Inventor); Ounaies, Zoubeida (Inventor)

    2004-01-01

    The invention described herein supplies a new class of electroactive polymeric blend materials which offer both sensing and actuation dual functionality. The blend comprises two components, one component having a sensing capability and the other component having an actuating capability. These components should be co-processable and coexisting in a phase separated blend system. Specifically, the materials are blends of a sensing component selected from the group consisting of ferroelectric, piezoelectric, pyroelectric and photoelectric polymers and an actuating component that responds to an electric field in terms of dimensional change. Said actuating component includes, but is not limited to, electrostrictive graft elastomers, dielectric electroactive elastomers, liquid crystal electroactive elastomers and field responsive polymeric gels. The sensor functionality and actuation functionality are designed by tailoring the relative fraction of the two components. The temperature dependence of the piezoelectric response and the mechanical toughness of the dual functional blends are also tailored by the composition adjustment.

  15. Organometallic polymerization catalysts

    SciTech Connect

    Waymouth, R.M.

    1993-12-31

    Well-defined transition metal catalysts have resulted in exciting new opportunities in polymer synthesis. The stereochemistry of vinyl polymers can be rationally controlled with choice of the appropriate catalysts. Studies with optically active catalyst precursors have revealed considerable information on the absolute stereochemistry of olefin polymerization and have led to the synthesis of novel chiral polyolefins. The development of homogeneous olefin metathesis catalysts has also led to a variety of well-defined new polymer structures with controlled molecular weight and molecular weight distribution. Recent advances in understanding the mechanisms and stereochemistry of homogeneous transition metal catalyzed polymerization will be discussed. The ability to control polymer structure through catalyst design presents exciting opportunities in the synthesis of {open_quotes}tailor-made{close_quotes} macromolecules.

  16. Surface polymerization agents

    SciTech Connect

    Taylor, C.; Wilkerson, C.

    1996-12-01

    This is the final report of a 1-year, Laboratory-Directed R&D project at LANL. A joint technical demonstration was proposed between US Army Missile Command (Redstone Arsenal) and LANL. Objective was to demonstrate that an unmanned vehicle or missile could be used as a platform to deliver a surface polymerization agent in such a manner as to obstruct the filters of an air-breathing mechanism, resulting in operational failure.

  17. Frontal Polymerization in Microgravity

    NASA Technical Reports Server (NTRS)

    Pojman, John A.

    1999-01-01

    Frontal polymerization systems, with their inherent large thermal and compositional gradients, are greatly affected by buoyancy-driven convection. Sounding rocket experiments allowed the preparation of benchmark materials and demonstrated that methods to suppress the Rayleigh-Taylor instability in ground-based research did not significantly affect the molecular weight of the polymer. Experiments under weightlessness show clearly that bubbles produced during the reaction interact very differently than under 1 g.

  18. Physicochemical Properties of 'Particle Brush'-Based Materials: Using Polymer Graft Modification to Tailor Particle Interactions

    NASA Astrophysics Data System (ADS)

    Schmitt, Michael D.

    The advent of surface-initiated controlled radical polymerization techniques has allowed a new class of hybrid polymer-grafted nanoparticles, known as eparticle brushes,f to be realized. By grafting polymers from the surface, interactions between particles can be tuned using the precise control over graft architecture (i.e. chain length, dispersity, particle size, and grafting density) afforded by controlled radical polymerizations. Previously, a transition from particle-like to polymer-like interactions in small particles with increasing graft length has been observed. In the limit of long graft lengths, the polymer chains impart new interactions between particles, such as entanglements. These results outline a rich, but largely unexplored parameter space. The present thesis further elucidates the extent to which polymer graft modification facilitates new interaction types between particles and the dependence of those interactions on chain conformation. Specifically, the mechanical properties, processability, phase separation, and vibrational modes of particle brushes are examined. A dependence of the mechanical properties of particle brush assemblies on particle size is accurately captured by accounting for differences in chain conformation between particles of different sizes using a simple scaling model. Further tailoring of mechanical characteristics in weak particle brush assemblies can be achieved using appropriate homopolymer additives to form two-component systems. Improved mechanical properties are accompanied by a significant enhancement in particle processability that allows application of previously unusable processing methods. Considering more complex systems, mesoscale phase separation of nanoparticles is demonstrated for the first time by blending of particle brushes with different graft polymers. Polymer graft modification is seen to not only strengthen and introduce new interactions, but also tune particle properties. Vibrational modes of particles are softened using graft modification with the chemical confinement of surface-grafted chains inducing tunable hybridization gaps in solid assemblies fabricated by facile methods. Particle brushes offer a unique opportunity to form complex, functional material systems from simple building blocks that demonstrate a range of unique, tunable properties pertinent to applications from optical computing to phononics and lighting.

  19. Durability of Polymeric Glazing and Absorber Materials

    SciTech Connect

    Jorgensen, G.; Terwilliger, K.; Bingham, C.; Milbourne, M.

    2005-01-01

    The Solar Heating and Lighting Program has set the goal of reducing the cost of solar water heating systems by at least 50%. An attractive approach to such large cost reduction is to replace glass and metal parts with less-expensive, lighter-weight, more-integrated polymeric components. The key challenge with polymers is to maintain performance and assure requisite durability for extended lifetimes. The objective of this task is to quantify lifetimes through measurement of the optical and mechanical stability of candidate polymeric glazing and absorber materials. Polycarbonate sheet glazings, as proposed by two industry partners, have been tested for resistance to UV radiation with three complementary methods. Incorporation of a specific 2-mil thick UV-absorbing screening layer results in glazing lifetimes of at least 15 years; improved screens promise even longer lifetimes. Proposed absorber materials were tested for creep and embrittlement under high temperature, and appear adequate for planned ICS absorbers.

  20. Biodegradable Multiamine Polymeric Vector for siRNA Delivery.

    PubMed

    Yuan, Yuanyuan; Gong, Faming; Cao, Yang; Chen, Weicai; Cheng, Du; Shuai, Xintao

    2015-04-01

    The gene silencing activity of small interfering RNA (siRNA) has led to their use as tools for target validation and as potential therapeutics for a variety of diseases. A major challenge is the development of vectors with high delivery efficiency and low toxicity. Although poly(ethylenimine) (PEI) has been regarded as the most promising polymeric vector for nucleic acid delivery, the nonbiodegradable structure greatly hinders its clinical application. In the present study, a diblock copolymer, PEG-PAsp(DIP-DETA), of poly(ethylene glycol) (PEG) and poly(L-aspartic acid) (PAsp) randomly grafted with pH-sensitive 2-(diisopropylamino)ethylamine (DIP) and diethylenetriamine (DETA) groups was synthesized via ring-opening polymerization and aminolysis reaction. Similar to polyethylenimine (PEI), the copolymer possesses a multiamine structure that not only allows effective siRNA complexation at neutral pH but also facilitates lysosomal release of siRNA via a proton buffering effect. Moreover, the poly(L-aspartic acid) backbone renders the vector biodegradability, which is not achievable with PEI. This novel polymeric vector can mediate effective intracellular siRNA delivery in various cancer cells. Consequently, the delivery of BCL-2 siRNA resulted in target gene silencing, inducing apoptosis and inhibiting the growth of cancer cells. These results show the potential of this non-PEI based polymeric vector with proton buffering capacity and biodegradability for siRNA delivery in cancer therapy. PMID:26310073

  1. Nanostructured and Surface Polymerized Iron Particles for Magnetorheological Fluids

    NASA Astrophysics Data System (ADS)

    Hu, Ben; Fuchs, Alan; Gordaninejad, Faramarz; Evrensel, Cahit

    A novel magnetorheological fluid, in which the surface of iron particles is coated with poly (butyl acrylate) by surface initiated atom transfer radical polymerization (ATRP), is investigated. The polymer coating procedure includes two steps, which are immobilization of initiator: 2-4(-chlorosulfonylphenyl)-ethytrichlorosilane (CTCS) on the iron particles surface and graft polymerization of butyl acrylate from the surface. The surface coating is characterized by FTIR and SEM. This magnetorheological fluid has controllable off-state viscosity and high shear yield stress. Coating polymer on the iron particles surface by ATRP can significantly reduce iron particles settling and improve stability of the MR fluid. Polymerization kinetics of bulk butyl acrylate are investigated using differential scanning calorimetry (DSC). Glass transition temperature is obtained using the step-scan DSC method. The molecular weight and conversion can be controlled by the molar ratio of monomer to initiator, reaction temperature and time. The reaction is first order determined by the plot of In (M/M0) against polymerization time. The overall activation energy is found to be 126kJ/mol by Kissinger's Method.

  2. Synthesis of perm-selective membranes by grafting acrylic acid into air-irradiated Teflon-FEP films

    NASA Astrophysics Data System (ADS)

    Bozzi, Annick; Chapiro, Adolphe

    Grafting acrylic acid into air-irradiated Teflon-FEP films was investigated. Pre-irradiation doses ranged from 0.5 to 10 kGy. Grafting occurred at 45 or 60°C. Homopolymerization inhibitors, ferrous ions or methylene blue, were added to the system. It was found that after completion of the reaction, within 40-100 min, membranes were obtained with very low electric resistivities. The influence of added inhibitors, pre-irradiation dose and grafting temperature was studied. From the results it is concluded that the initiating centers in air-irradiated Teflon-FEP are, on the one hand, peroxides of structure POOP', in which P is a polymeric radical and Pprime; a small fragment, and on the other trapped PO .2 radicals. The latter only react after losing their oxygen. In the presence of polymerization inhibitors, initiation involves a redox process which reduces the overall activation energy.

  3. An ultra-sensitive microfluidic immunoassay using living radical polymerization and porous polymer monoliths.

    SciTech Connect

    Abhyankar, Vinay V.; Singh, Anup K.; Hatch, Anson V.

    2010-07-01

    We present a platform that combines patterned photopolymerized polymer monoliths with living radical polymerization (LRP) to develop a low cost microfluidic based immunoassay capable of sensitive (low to sub pM) and rapid (<30 minute) detection of protein in 100 {micro}L sample. The introduction of LRP functionality to the porous monolith allows one step grafting of functionalized affinity probes from the monolith surface while the composition of the hydrophilic graft chain reduces non-specific interactions and helps to significantly improve the limit of detection.

  4. Venturi grafts for hemodialysis access.

    PubMed

    Drasler, W J; Wilson, G J; Jenson, M L; Klement, P; George, S A; Protonotarios, E I; Dutcher, R G; Possis, Z C

    1990-01-01

    Vascular access grafts can produce venous and puncture site stenosis, and excessive shunted flow. A vascular access graft that controls the shunted flow at 500-650 ml/min by venturi flow resistance, and offers the potential for reduced venous stenosis, is presented. Twelve venturi grafts consisting of 6 mm ePTFE, with a thermally formed venturi resistance, were implanted in a canine femoral arterio-venous (A-V) model and cannulated for simulated dialysis for periods up to 6 months. Pressures, bleeding times, and puncture site healing were compared at sites upstream and downstream of the venturi. Nine 6 mm ePTFE grafts were implanted as controls. Venturi and control graft patency rates were similar: 90% for venturi grafts and 89% for control implants at 4 months. Measurements verified pressure dissipation by the venturi from 85 to 15 mmHg, delivering near-normal pressures to the vein; downstream pressures were 22 mmHg higher in controls. Sites downstream of the venturi did not bleed at 4 min, whereas bleeding was often noted after 9 min at other sites. Puncture sites upstream of the venturi had less stenosis and less mural thrombus than sites downstream of the venturi, and compared favorably with puncture sites in the control grafts. This improved healing and low pressure delivery to the vein may offer clinical advantages. PMID:2252803

  5. Self-assembly of well-defined polyacrylamide-polystyrene copolymer on fibrillar clays via ultrasonic-assisted surface-initiated atom transfer radical polymerization.

    PubMed

    Liu, Peng; Wang, Tingmei; Su, Zhixing

    2006-06-01

    Well-defined polyacrylamide-polystyrene copolymers were grafted from the fibrillar clay, attapulgite, by a four-step self-assembly process: (i) the gamma-aminopropyltriethoxyl silane was self-assembled onto the surfaces of the attapulgite; (ii) the surface amino groups were amidated with bromoacetylbromide; (iii) the bromo-acetamide modified attapulgite was used as macro-initiator for the surface-initiated atom transfer radical polymerization of styrene with the catalyst of the complex of 1,10-phenanthroline and Cu(I)Br; (iv) the polystyrene grafted attapulgite was then used as macroinitiator for the polymerization of acrylamide. The two steps of the surface-initiated atom transfer radical polymerizations were all conducted under ultrasonic irradiation at room temperature. The product, polyacrylamide-polystyrene copolymers grafted attapulgite, had been characterized with elemental analysis, Fourier transform infrared spectroscopy, Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy. PMID:17025071

  6. Robot-Assisted Antegrade In-Situ Fenestrated Stent Grafting

    SciTech Connect

    Riga, Celia V. Bicknell, Colin D.; Wallace, Daniel; Hamady, Mohamad; Cheshire, Nicholas

    2009-05-15

    To determine the technical feasibility of a novel approach of in-situ fenestration of aortic stent grafts by using a remotely controlled robotic steerable catheter system in the porcine model. A 65-kg pig underwent robot-assisted bilateral antegrade in-situ renal fenestration of an abdominal aortic stent graft with subsequent successful deployment of a bare metal stent into the right renal artery. A 16-mm iliac extension covered stent served as the porcine aortic endograft. Under fluoroscopic guidance, the graft was punctured with a 20-G customized diathermy needle that was introduced and kept in place by the robotic arm. The needle was exchanged for a 4 x 20 mm cutting balloon before successful deployment of the renal stent. Robot-assisted antegrade in-situ fenestration is technically feasible in a large mammalian model. The robotic system enables precise manipulation, stable positioning, and minimum instrumentation of the aorta and its branches while minimizing radiation exposure.

  7. Secondary alveolar bone grafting: our experience with olecranon bone graft.

    PubMed

    Nadal, Emmanuela; Sabás, Mariana; Dogliotti, Pedro; Espósito, Raquel

    2010-03-01

    Management of alveolar cleft has dramatically changed during the last century: secondary alveolar bone grafting is now an integral part of cleft palate and craniofacial center's protocols. The objectives of alveolar repair and bone grafting are as follows: providing a continuous and stable maxillary dental arch, closure of oronasal fistulae, adequate bone for tooth eruption or orthodontic movement, and nasal base support, improving facial aesthetic. Although cancellous iliac bone is the donor site selected more frequently, bone grafts harvested from different sites have been advocated to decrease donor site morbidity.The aim of this study was to propose and evaluate the use of olecranon as a donor site in 24 patients with secondary alveolar cleft. The graft is taken as a single piece to fit the alveolar cleft defect, and it includes periosteum and corticocancellous bone to improve early vascularization and greater volume maintenance. PMID:20186086

  8. Polymer grafted hydroxyapatite whisker as a filler for dental composite resin with enhanced physical and mechanical properties.

    PubMed

    Liu, Fengwei; Wang, Ruili; Cheng, Yanhua; Jiang, Xiaoze; Zhang, Qinghong; Zhu, Meifang

    2013-12-01

    The objective of this study was to investigate the effect of surface graft polymerization of hydroxyapatite whisker (HW) on physical and mechanical properties of dental composite resin. Poly bisphenol A glycidyl methacrylate (Poly(Bis-GMA)) was grafted onto silanized hydroxyapatite whisker (SHW) via solution polymerization and the amount of the Poly(Bis-GMA) on the surface was effectively controlled by polymerization time. The obtained poly(Bis-GMA) grafted hydroxyapatite whisker (PGHW) with different polymer contents was filled into a resin matrix respectively, meanwhile the composites with HW and with SHW served as controls. Monomer conversion was characterized by Fourier transform infrared spectroscopy (FTIR) and volume shrinkage of the composite resin was measured with a density tester. Mechanical properties were tested with a universal testing machine. The results indicated that the composite filled with PGHW-1h (graft ratio of poly(Bis-GMA): 8.5 wt.%) showed lower shrinkage and better mechanical properties, improving flexural strength by 6.5% and 11.9% compared with SHW filled composite and HW filled composite, respectively. However, PGHW with higher graft ratios aggregated seriously and formed defects in the composite, leading to deterioration of mechanical properties. It was revealed that the poly(Bis-GMA) on the surface of PGHW acted as a functional transition layer and enhanced interfacial compatibility and interaction between whisker and resin matrix, which facilitated the dispersion of PGHW in the composite and decreased the composite shrinkage. Thus, the graft polymerization of Bis-GMA on the surface of filler might be a promising modification method for the fabrication of dental materials. PMID:24094216

  9. Actin polymerization-enhancing drugs promote ovarian follicle growth mediated by the Hippo signaling effector YAP.

    PubMed

    Cheng, Yuan; Feng, Yi; Jansson, Lina; Sato, Yorino; Deguchi, Masashi; Kawamura, Kazuhiro; Hsueh, Aaron J

    2015-06-01

    Hippo signaling pathway consists of conserved serine/threonine kinases to maintain optimal organ sizes. Studies have demonstrated that fragmentation of murine ovaries increases actin polymerization and disrupts Hippo signaling, leading to nuclear translocation of Hippo signaling effector Yes-associated protein (YAP) in ovarian follicles and follicle growth. For patients with polycystic ovarian syndrome showing follicle arrest, ovarian wedge resection and laser drilling promote follicle growth. Because these damaging procedures likely involve actin polymerization, we tested whether actin polymerization-promoting drugs could promote YAP translocation and stimulate follicle growth. Treatment of murine ovaries with μM Jasplakinolide (JASP), an actin polymerization-promoting cyclic peptide, or sphingosine-1-phosphate (S1P), a follicular fluid constituent known to promote actin polymerization, increased the conversion of globular actin to the filamentous form, followed by increased nuclear YAP and expression of downstream connective tissue growth factor (CCN2). After short-term treatments with JASP or S1P, in vitro cultured and in vivo grafted ovaries showed follicle growth. Furthermore, induction of constitutively active YAP in ovarian grafts of transgenic mice enhanced follicle development, whereas treatment of human ovarian cortices with JASP or S1P increased CCN2 expression. Thus, JASP and S1P stimulate follicle growth and are potential therapeutic agents for treating polycystic ovarian syndrome and other ovarian disorders. PMID:25690654

  10. Grafting PMMA Brushes from α-Alumina Nanoparticles via SI-ATRP.

    PubMed

    Khabibullin, Amir; Bhangaonkar, Karan; Mahoney, Clare; Lu, Zhao; Schmitt, Michael; Sekizkardes, Ali Kemal; Bockstaller, Michael R; Matyjaszewski, Krzysztof

    2016-03-01

    Alumina nanoparticles are widely used as nanofillers for polymer nanocomposites. Among several different polymorphs of alumina, α-alumina has the most desirable combination of physical properties. Hence, the attachment of polymer chains to α-alumina to enhance compatibility in polymeric matrixes is an important goal. However, the chemical inertness and low concentration of surface hydroxyl groups have rendered polymer modification of α-alumina a long-standing challenge. Herein, we report that activation of α-alumina in concentrated or molten NaOH as well as in molten K2S2O7 increased polymer graft density up to 50%, thereby facilitating the synthesis of α-alumina brush particles with uniform grafting density of 0.05 nm(-2) that are readily miscible or dispersible in organic solvents or in chemically compatible polymeric hosts. PMID:26901494

  11. Fat Grafting for Facial Filling and Regeneration.

    PubMed

    Coleman, Sydney R; Katzel, Evan B

    2015-07-01

    Plastic surgeons have come to realize that fat grafting can rejuvenate an aging face by restoring or creating fullness. However, fat grafting does much more than simply add volume. Grafted fat can transform or repair the tissues into which it is placed. Historically, surgeons have hesitated to embrace the rejuvenating potential of fat grafting because of poor graft take, fat necrosis, and inconsistent outcomes. This article describes fat grafting techniques and practices to assist readers in successful harvesting, processing, and placement of fat for optimal graft retention and facial esthetic outcomes. PMID:26116934

  12. Bio-Inspired Renewable Surface-Initiated Polymerization from Permanently Embedded Initiators.

    PubMed

    Du, Tao; Li, Bin; Wang, Xiaolong; Yu, Bo; Pei, Xiaowei; Huck, Wilhelm T S; Zhou, Feng

    2016-03-18

    Herein, we describe a simple and robust approach to repeatedly modify surfaces with polymer brushes through surface-initiated atomic transfer radical polymerization (SI-ATRP), based on an initiator-embedded polystyrene sheet that does not rely on specific surface chemistries for initiator immobilization. The surface-grafted polymer brushes can be wiped away to expose fresh underlying initiator that re-initiates polymerization. This strategy provides a facile route for modification of molded or embossed surfaces, with possible applications in the preparation of fluidic devices and polymer-embedded circuits. PMID:26915991

  13. Polymerization Evaluation by Spectrophotometric Measurements.

    ERIC Educational Resources Information Center

    Dunach, Jaume

    1985-01-01

    Discusses polymerization evaluation by spectrophotometric measurements by considering: (1) association degrees and molar absorptivities; (2) association degrees and equilibrium constants; and (3) absorbance and equilibrium constants. (JN)

  14. Polymeric salt bridges for conducting electric current in microfluidic devices

    DOEpatents

    Shepodd, Timothy J.; Tichenor, Mark S.; Artau, Alexander

    2009-11-17

    A "cast-in-place" monolithic microporous polymer salt bridge for conducting electrical current in microfluidic devices, and methods for manufacture thereof is disclosed. Polymeric salt bridges are formed in place in capillaries or microchannels. Formulations are prepared with monomer, suitable cross-linkers, solvent, and a thermal or radiation responsive initiator. The formulation is placed in a desired location and then suitable radiation such as UV light is used to polymerize the salt bridge within a desired structural location. Embodiments are provided wherein the polymeric salt bridges have sufficient porosity to allow ionic migration without bulk flow of solvents therethrough. The salt bridges form barriers that seal against fluid pressures in excess of 5000 pounds per square inch. The salt bridges can be formulated for carriage of suitable amperage at a desired voltage, and thus microfluidic devices using such salt bridges can be specifically constructed to meet selected analytical requirements.

  15. Bimorphic polymeric photomechanical actuator

    NASA Technical Reports Server (NTRS)

    Sarkisov, Sergey S. (Inventor); Curley, Michael J. (Inventor); Adamovsky, Grigory (Inventor); Sarkisov, Jr., Sergey S. (Inventor); Fields, Aisha B. (Inventor)

    2006-01-01

    A bimorphic polymeric photomechanical actuator, in one embodiment using polyvinylidene fluoride (PVDF) as a photosensitive body, transmitting light over fiber optic cables, and controlling the shape and pulse duration of the light pulse to control movement of the actuator. Multiple light beams are utilized to generate different ranges of motion for the actuator from a single photomechanical body and alternative designs use multiple light beams and multiple photomechanical bodies to provide controlled movement. Actuator movement using one or more ranges of motion is utilized to control motion to position an actuating element in three dimensional space.

  16. Continuous polymerization reactor

    SciTech Connect

    Wilt, M.S.

    1986-05-06

    A method is described for contacting olefinic monomer and initiator in a continuous polymerization process comprising of the steps of: creating three turbulent zones in a vessel; introducing the olefinic monomer into a first part of the periphery of each one of the three turbulent zones; introducing the initiator into a second part of the periphery of each one of the three turbulent zones, wherein the first part of the periphery of each one of the three turbulent zones is substantially diametrically opposed to the second part of the periphery of each one of the three turbulent zones respectively.

  17. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  18. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Bauman, Robert

    2006-11-14

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  19. Living olefin polymerization processes

    DOEpatents

    Schrock, R.R.; Baumann, R.

    1999-03-30

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  20. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    2003-08-26

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  1. Polymeric battery separators

    SciTech Connect

    Minchak, R. J.; Schenk, W. N.

    1985-06-11

    Configurations of cross-linked or vulcanized amphophilic or quaternized block copolymer of haloalkyl epoxides and hydroxyl terminated alkadiene polymers are useful as battery separators in both primary and secondary batteries, particularly nickel-zinc batteries. The quaternized block copolymers are prepared by polymerizing a haloalkyl epoxide in the presence of a hydroxyl terminated 1,3-alkadiene to form a block copolymer that is then reacted with an amine to form the quaternized or amphophilic block copolymer that is then cured or cross-linked with sulfur, polyamines, metal oxides, organic peroxides and the like.

  2. Synthesis and characterization of macromolecular layers grafted to polymer surfaces

    NASA Astrophysics Data System (ADS)

    Burtovyy, Oleksandr

    The composition and behavior of surfaces and interfaces play a pivotal role in dictating the overall efficiency of the majority of polymeric materials and devices. Surface properties of the materials can be altered using surface modification techniques. It is necessary to highlight that successful methods of surface modification should affect only the upper layer of the polymer material without changing bulk properties. The processes must introduce new functionalities to the surface, optimize surface roughness, lubrication, hydrophobicity, hydrophilicity, adhesion, conductivity, and/or biocompatibility. Research presented in this dissertation is dedicated to the synthesis, characterization, and application of thin macromolecular layers anchored to polymer substrates. Specifically, attachment of functional polymers via a "grafting to" approach has been extensively studied using PET and nylon model substrates. First, poly(glycidyl methacrylate) was used to introduce permanent functionalities to the model substrates by anchoring it to model films. Then, three different functional polymers were grafted on top of the previous layer. As one part of this study, the temperature and time dependence of grafting functional layers were studied. The surface coverage by hydrophobic polymer was determined from experimental data and predicted by a model. In general, the model has a high degree of predictive capability. Next, surface modification of polymeric fibers and membranes is presented as an important application of the polymer thin layers targeted in the study. Specifically, the procedures developed for surface modification of model substrates was employed for modification of PET, nylon, and cotton fabrics as well as PET track-etched membranes. Since epoxy groups are highly reactive in various chemical reactions, the approach becomes virtually universal, allowing both various surfaces and end-functionalized macromolecules to be used in the grafted layer synthesis. PET membranes modified with a reactive anchoring layer can be successfully used to build membrane assemblies by incorporating silica, aluminum, or titanium oxide microparticles as spacers. It is expected that the proposed approaches for the surface modification of the membranes and for the generation of multilayered membrane assemblies can be employed straightforwardly to provide an efficient platform for fabrication of breathable protective materials. Characterization of modified membranes with a cantilever-based method, which can be used for prediction of properties and behavior of thin grafted films, is reported. This technique can be used as a method for fast screening of modified membranes. The method is very robust and capable of detecting very small quantities of substance adsorbed; kinetics of the process can be tracked, as well. This approach can be further developed as a handheld sensor for early warning of the presence of chemical vapors and nerve agents.

  3. Bone Grafting: Sourcing, Timing, Strategies, and Alternatives.

    PubMed

    Egol, Kenneth A; Nauth, Aaron; Lee, Mark; Pape, Hans-Christoph; Watson, J Tracy; Borrelli, Joseph

    2015-12-01

    Acute fractures, nonunions, and nonunions with bone defects or osteomyelitis often need bone graft to facilitate union. There are several factors to consider when it is determined that a bone graft is needed. These factors include the source of the bone graft (autograft vs. allograft), proper timing for placement of the bone graft, strategies to avoid further complications (particularly in the setting of osteomyelitis), and with the development of a variety of bone graft substitutes, whether alternatives to autograft are available and appropriate for the task at hand. Autograft bone has commonly been referred to as the "gold standard" of bone grafts, against which the efficacy of other grafts has been measured. The best timing for when to place a bone graft or substitute is also somewhat controversial, particularly after an open fracture or a potentially contaminated bed. The treatment of infected nonunions, particularly those that require a graft to facilitate healing, can be quite challenging. Typically, the infection is completely eradicated before placement of a bone graft, but achieving a sterile bed and the timing of a bone graft require strategic thinking and planning. This review outlines the benefits of autografts, the most suitable sites for harvesting bone grafts, the timing of bone graft procedures, the potential risks and benefits of grafting in the face of infection, and the currently available bone graft extenders. PMID:26584259

  4. Experience of injected fat grafting.

    PubMed

    Matsudo, P K; Toledo, L S

    1988-02-01

    Eighteen months' experience with the injected fat grafting technique used in 208 patients to correct various problems such as buttocks (augmentation and reshaping), trochanteric depressions, breast augmentation, scar depressions, thighs and legs (calf and ankle augmentation), small wrinkles and depressions of the face (Romberg's disease), nasolabial fold, upper outer breast quadrant, liposuction sequela, fingers and hands is presented. This method shows major advantages with few complications. Some technical details and recommendations for successful fat grafting are also presented. PMID:3376783

  5. Reoperation after coronary bypass grafting.

    PubMed Central

    Menkis, A. H.; Carley, S. D.; Clough, T. M.

    1993-01-01

    Coronary artery bypass grafting is one of the most commonly performed surgical procedures in the western world, and myocardial revascularization during the first operation is well established. But patients are now surviving beyond the patency of their primary grafts. Repeat myocardial revascularization can be performed successfully in patients who have adequate ventricular function and graftable distal vessels. Images Figures 1-2 Figure 3 Figure 5 PMID:8495123

  6. Preparation of metal adsorbent from poly(methyl acrylate)-grafted-cassava starch via gamma irradiation

    NASA Astrophysics Data System (ADS)

    Suwanmala, Phiriyatorn; Hemvichian, Kasinee; Hoshina, Hiroyuki; Srinuttrakul, Wannee; Seko, Noriaki

    2012-08-01

    Metal adsorbent containing hydroxamic acid groups was successfully synthesized by radiation-induced graft copolymerization of methyl acrylate (MA) onto cassava starch. The optimum conditions for grafting were studied in terms of % degree of grafting (Dg). Conversion of the ester groups present in poly(methyl acrylate)-grafted-cassava starch copolymer into hydroxamic acid was carried out by treatment with hydroxylamine (HA) in the presence of alkaline solution. The maximum percentage conversion of the ester groups of the grafted copolymer, % Dg=191 (7.63 mmol/g of MA), into the hydroxamic groups was 70% (5.35 mmol/g of MA) at the optimum condition. The adsorbent of 191%Dg had total adsorption capacities of 2.6, 1.46, 1.36, 1.15 and 1.6 mmol/g-adsorbent for Cd2+, Al3+, UO22+, V5+ and Pb2+, respectively, in the batch mode adsorption.

  7. Grafting of HEMA onto dopamine coated stainless steel by 60Co-γ irradiation method

    NASA Astrophysics Data System (ADS)

    Jin, Wanqin; Yang, Liming; Yang, Wei; Chen, Bin; Chen, Jie

    2014-12-01

    A novel method for grafting of 2-hydroxyethyl methacrylate (HEMA) onto the surface of stainless steel (SS) was explored by using 60Co-γ irradiation. The surface of SS was modified by coating of dopamine before radiation grafting. The grafting reaction was performed in a simultaneous irradiation condition. The chemical structures change of the surface before and after grafting was demonstrated by Fourier transform infrared (FTIR) spectrometer. The hydrophilicity of the samples was determined by water contact angle measurement in the comparison of the stainless steel in the conditions of pristine, dopamine coated and HEMA grafted. Surface morphology of the samples was characterized by atomic force microscope (AFM) and scanning electron microscope (SEM). The corrosion resistance properties of the samples were evaluated by Tafel polarization curve. The hemocompatibility of the samples were tested by platelet adhesion assay.

  8. Encapsulation of clozapine in polymeric nanocapsules and its biological effects.

    PubMed

    Łukasiewicz, Sylwia; Szczepanowicz, Krzysztof; Podgórna, Karolina; Błasiak, Ewa; Majeed, Nather; Ogren, Sven Ove Ögren; Nowak, Witold; Warszyński, Piotr; Dziedzicka-Wasylewska, Marta

    2016-04-01

    Clozapine is an effective atypical antipsychotic drug that unfortunately exhibits poor oral bioavailability. Moreover, the clinical use of the compound is limited because of its numerous unfavorable and unsafe side effects. Therefore, the aim of the present study was the development of a new nanocarrier for a more effective clozapine delivery. Here, clozapine was encapsulated into polymeric nanocapsules (NCs). Polyelectrolyte multilayer shells were constructed by the technique of sequential adsorption of polyelectrolytes (LbL) using biocompatible polyanion PGA (Poly-l-glutamic acid, sodium salt) and polycation PLL (poly-l-lysine) on clozapine-loaded nanoemulsion cores. Pegylated external layers were prepared using PGA-g-PEG (PGA grafted by PEG (polyethylene glycol)). Clozapine was successfully loaded into the PLL-PGA nanocarriers (CLO-NCs) with an average size of 100nm. In vitro analysis of the interactions of the CLO-NCs with the cells of the mononuclear phagocytic system (MPS) was conducted. Cell biocompatibility, phagocytosis potential, and cellular uptake were studied. Additionally, the biodistribution and behavioral effects of the encapsulated clozapine were also studied. The results indicate that surface modified (by PEG grafting) polymeric PLL-PGA CLO-NCs are very promising nanovehicles for improving clozapine delivery. PMID:26774571

  9. Costal Grafting in Mandibular Reconstruction

    PubMed Central

    Bourlet, Jerôme; Château, Joseph; Jacquemart, Mathieu; Dufour, Clémence; Mojallal, Ali; Gleizal, Arnaud

    2015-01-01

    Background: Reconstruction of mandibular bone defect is a common indication in craniomaxillofacial surgery, and free fibular flap is the gold standard for this indication. However, there are alternatives; nonvascular bone grafting is one of them, and we present the costal grafting for mandibular reconstruction, a classic technique that is reliable, efficient, and produced less morbidity than the technique of using composite free flaps. Method: A 9-year retrospective review of 54 patients treated surgically for mandibular reconstruction was performed. The criterion mainly analyzed was graft survival. The surgical technique was described in detail. Results: A total of 54 patients with mandibular bone defect were identified. Five symphysis, 46 corpus, and 20 ramus defects were considered. These patients underwent reconstruction by costal grafting, and the engrafting was successful in 92.6% of cases. Dental rehabilitation with dental implants was realized in 70% of cases. Conclusions: The approach described in this article allowed the authors to obtain good results with costal grafting for mandibular reconstruction and dental rehabilitation. Costal grafting is a good alternative for fibula free flap in specific indications. Reconstruction of mandibular bone defect is a common indication in craniomaxillofacial surgery. Since the 1980s, the gold standard for these defects is the use of free fibular flap.1 In some cases, this technique is contradicted; the surgeon then has several possibilities for the use of free osteomyocutaneous flaps (iliac crest, scapula, and serrato-costal flaps).2–8 PMID:26893990

  10. Bilateral internal thoracic artery grafting

    PubMed Central

    2013-01-01

    The effectiveness of the left internal mammary artery graft to the anterior descending coronary artery as a surgical strategy has been shown to improve the survival rate and decrease the risk of adverse cardiac events in patients undergoing coronary bypass surgery. These clinical benefits appear to be related to the superior short and long-term patency rates of the internal thoracic artery graft. Although the advantages of using of both internal thoracic arteries (ITA) for bypass grafting have taken longer to prove, recent results from multiple data sets now support these findings. The major advantage of bilateral ITA grafting appears to be improved survival rate, while the disadvantages of complex ITA grafting include the increased complexity of operation, and an increased risk of wound complications. While these short-term disadvantages have been mitigated in contemporary surgical practice, they have not eliminated. Bilateral ITA grafting should be considered the procedure of choice for patients undergoing coronary bypass surgery that have a predicted survival rate of longer than ten years. PMID:23977627

  11. FAS grafted superhydrophobic ceramic membrane

    NASA Astrophysics Data System (ADS)

    Lu, Jun; Yu, Yun; Zhou, Jianer; Song, Lixin; Hu, Xingfang; Larbot, Andre

    2009-08-01

    The hydrophobic properties of γ-Al 2O 3 membrane have been obtained by grafting fluoroalkylsilane (FAS) on the surface of the membrane. The following grafting parameters were studied: the eroding time of the original membrane, the grafting time, the concentration of FAS solution and the multiplicity of grafting. Hydrophobicity of the membranes was characterized by contact angle (CA) measurement. The thermogravimetric analysis (TGA) was used to investigate the weight loss process (25-800 °C) of the fluoroalkylsilane grafted on Al 2O 3 powders under different grafting conditions. The morphologies of the membranes modified under different parameters were examined by field emission scanning electron microscopy (FE-SEM) and the surface roughness (Ra) was measured using white light interferometers. A needle-like structure was observed on the membrane surface after modification, which causes the change of Ra. On the results above, we speculated a model to describe the reaction between FAS and γ-Al 2O 3 membrane surface as well as the formed surface morphology.

  12. PLLA-grafted cellulose nanocrystals: Role of the CNC content and grafting on the PLA bionanocomposite film properties.

    PubMed

    Lizundia, Erlantz; Fortunati, Elena; Dominici, Franco; Vilas, José Luis; León, Luis Manuel; Armentano, Ilaria; Torre, Luigi; Kenny, Josè M

    2016-05-20

    Cellulose nanocrystals (CNC), extracted from microcrystalline cellulose by acid hydrolysis, were grafted by ring opening polymerization of l-Lactide initiated from the hydroxyl groups available at their surface and two different CNC:l-lactide ratios (20:80 and 5:95) were obtained. The resulting CNC-g-PLLA nanohybrids were incorporated in poly(lactic acid) (PLA) matrix by an optimized extrusion process at two different content (1wt.% and 3wt.%) and obtained bionanocomposite films were characterized by thermal, mechanical, optical and morphological properties. Thermal analysis showed CNC grafted with the higher ratio of lactide play a significant role as a nucleating agent. Moreover, they contribute to a significant increase in the crystallization rate of PLA, and the best efficiency was revealed with 3wt.% of CNC-g-PLLA. This effect was confirmed by the increased in Young's modulus, suggesting the CNC graft ratio and content contribute significantly to the good dispersion in the matrix, positively affecting the final bionanocomposite properties. PMID:26917380

  13. Binary mixed homopolymer brushes grafted on nanorod particles: A self-consistent field theory study

    SciTech Connect

    Ma, Xin; Yang, Yingzi; Tang, Ping E-mail: fengqiu@fudan.edu.cn; Qiu, Feng E-mail: fengqiu@fudan.edu.cn; Zhu, Lei; Zhao, Bin

    2013-12-07

    We employ the self-consistent field theory to study phase structures of brush-rod systems composed of two chemically distinct linear homopolymers. The polymer chains are uniformly grafted on the surface of a nanorod particle of finite length and comparable radius to the polymer radius of gyration. A “masking” technique treating the cylindrical boundary is introduced to solve the modified diffusion equations with an efficient and high-order accurate pseudospectral method involving fast Fourier transform on an orthorhombic cell. A rich variety of structures for the phase separated brushes is predicted. Phase diagrams involving a series of system parameters, such as the aspect ratio of the nanorod, the grafting density, and the chain length are constructed. The results indicate that the phase structure of the mixed brush-rod system can be tailored by varying the grafted chain length and/or the aspect ratio of the rod to benefit the fabrication of polymeric nanocomposites.

  14. Binary mixed homopolymer brushes grafted on nanorod particles: A self-consistent field theory study

    NASA Astrophysics Data System (ADS)

    Ma, Xin; Yang, Yingzi; Zhu, Lei; Zhao, Bin; Tang, Ping; Qiu, Feng

    2013-12-01

    We employ the self-consistent field theory to study phase structures of brush-rod systems composed of two chemically distinct linear homopolymers. The polymer chains are uniformly grafted on the surface of a nanorod particle of finite length and comparable radius to the polymer radius of gyration. A "masking" technique treating the cylindrical boundary is introduced to solve the modified diffusion equations with an efficient and high-order accurate pseudospectral method involving fast Fourier transform on an orthorhombic cell. A rich variety of structures for the phase separated brushes is predicted. Phase diagrams involving a series of system parameters, such as the aspect ratio of the nanorod, the grafting density, and the chain length are constructed. The results indicate that the phase structure of the mixed brush-rod system can be tailored by varying the grafted chain length and/or the aspect ratio of the rod to benefit the fabrication of polymeric nanocomposites.

  15. Space environmental effects on polymeric materials

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard L.; Orwoll, Robert A.

    1988-01-01

    Polymer-matrix composites have considerable potential for use in the construction of orbiting structures such as the space station and space antennas because of their light weight, high strength, and low thermal expansion. However, they can suffer surface erosion by interaction with atomic oxygen in low-Earth orbit and degradation and/or embrittlement by electrons and ultraviolet radiation especially in geosynchronous orbit. Thus, a study of the effect of these environmental hazards on polymeric materials is an important step in the assessment of such materials for future use in space.

  16. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. The highest conductivities reported (approximately 4/Scm) were achieved with polythiophene in a polystyrene host polymer. The best films using a polyamide as base polymer were four orders of magnitude less conductive than the polystyrene films. The authors suggested that this was because polyimides were unable to swell sufficiently for infiltration of monomer as in the polystyrene. It was not clear, however, if the different conductivities obtained were merely the result of differing oxidation conditions. Oxidation time, temperature and oxidant concentration varied widely among the studies.

  17. Modification of polysulfone membranes via surface-initiated atom transfer radical polymerization

    NASA Astrophysics Data System (ADS)

    Dong, Han-Bang; Xu, You-Yi; Yi, Zhuan; Shi, Jun-Li

    2009-08-01

    Hydrophilic poly((poly(ethylene glycol) methyl ether methacrylate) (P(PEGMA)) and poly(glycidylmethacrylate) (PGMA) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surfaces via surface-initiated atom transfer radical polymerization (ATRP). Prior to ATRP, chloromethylation of PSF was performed beforehand and the obtained CMPSF was prepared into porous membranes by phase inversion process. It was demonstrated that the benzyl chloride groups on the CMPSF membrane surface afforded effective macroinitiators to graft the well-defined polymer brushes. 1H NMR was employed to confirm the structure of CMPSF. The grafting yield of P(PEGMA) and PGMA was determined by weight gain measurement. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the grafting of P(PEGMA) and PGMA chains. Water contact angle measurements indicated that the introduction of P(PEGMA) and PGMA graft chains promoted remarkably the surface hydrophilicity of PSF membranes. The effects of P(PEGMA) and PGMA immobilization on membrane morphology, permeability and fouling resistance were investigated. It was found that P(PEGMA) and PGMA grafts brought higher pure water flux, improved hydrophilic surface and better anti-protein absorption ability to PSF membranes after modification. And evidently, macromonomer P(PEGMA) brought much better properties to the PSF membranes than PGMA macromonomer.

  18. Amplification of actin polymerization forces.

    PubMed

    Dmitrieff, Serge; Nédélec, François

    2016-03-28

    The actin cytoskeleton drives many essential processes in vivo, using molecular motors and actin assembly as force generators. We discuss here the propagation of forces caused by actin polymerization, highlighting simple configurations where the force developed by the network can exceed the sum of the polymerization forces from all filaments. PMID:27002174

  19. Coating of plasma polymerized film

    NASA Technical Reports Server (NTRS)

    Morita, S.; Ishibashi, S.

    1980-01-01

    Plasma polymerized thin film coating and the use of other coatings is suggested for passivation film, thin film used for conducting light, and solid body lubrication film of dielectrics of ultra insulators for electrical conduction, electron accessories, etc. The special features of flow discharge development and the polymerized film growth mechanism are discussed.

  20. Management of an infected aortic graft with endovascular stent grafting.

    PubMed

    Jamel, Sara; Attia, Rizwan; Young, Christopher

    2013-01-01

    Aortic graft infection, one of the most common fatal complications of aortovascular surgery, is managed mainly by the removal of infected graft material and re-establishment of vascular continuity using an extra-anatomical bypass or in situ graft replacement. Despite significant progress in perioperative, surgical, and medical treatments, the mortality and morbidity for this condition remain high. Here, we report the use of endograft implantation and prolonged intravenous antibiotics to successfully treat a life-threatening Dacron aortic tube graft infection and anastomotic leak. Although the gold standard is surgical removal of infected material and repair with a homograft, in certain extremely high-risk patients such as ours, an alternate strategy may be warranted when the risks associated with surgery are prohibitive. Endovascular repair of a surgical Dacron graft leak may provide a novel temporizing measure in the acute setting, allowing for delayed semi-urgent surgical intervention, or it may provide a definitive treatment, as in our case. At the four-year follow-up, our patient was well with a good quality of life and with no clinical, radiological, or biochemical evidence of infection. PMID:22641467

  1. Grafting titanium nitride surfaces with sodium styrene sulfonate thin films

    PubMed Central

    Zorn, Gilad; Migonney, Véronique; Castner, David G.

    2014-01-01

    The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm2. PMID:25280842

  2. Compliant electrospun silk fibroin tubes for small vessel bypass grafting.

    PubMed

    Marelli, Benedetto; Alessandrino, Antonio; Farè, Silvia; Freddi, Giuliano; Mantovani, Diego; Tanzi, Maria Cristina

    2010-10-01

    Processing silk fibroin (SF) by electrospinning offers a very attractive opportunity for producing three-dimensional nanofibrillar matrices in tubular form, which may be useful for a biomimetic approach to small calibre vessel regeneration. Bypass grafting of small calibre vessels, with a diameter less than 6mm, is performed mainly using autografts, like the saphenous vein or internal mammary artery. At present no polymeric grafts made of SF are commercially available, mainly due to inadequate properties (low compliance and lack of endothelium cells). The aim of this work was to electrospin SF into tubular structures (Ø=6mm) for small calibre vessel grafting, characterize the morphological, chemico-physical and mechanical properties of the electrospun SF structures and to validate their potential to interact with cells. The morphological properties of electrospun SF nanofibres were investigated by scanning electron microscopy. Chemico-physical analyses revealed an increase in the crystallinity of the structure of SF nanofibres on methanol treatment. Mechanical tests, i.e. compliance and burst pressure measurements, of the electrospun SF tubes showed that the inner pressure to radial deformation ratio was linear for elongation up to 15% and pressure up to 400 mm Hg. The mean compliance value between 80 and 120 mm Hg was higher than the values reported for both Goretex(R) and Dacron(R) grafts and for bovine heterografts, but still slightly lower than those of saphenous and umbilical vein, which nowadays represent the gold standard for the replacement of small calibre arteries. The electrospun tubes resisted up to 575+/-17 mmHg, which is more than four times the upper physiological pressure of 120 mmHg and more than twice the pathological upper pressures (range 180-220 mmHg). The in vitro tests showed a good cytocompatibility of the electrospun SF tubes. Therefore, the electrospun SF tubes developed within this work represent a suitable candidate for small calibre blood vessel replacement. PMID:20466080

  3. Poly(vinylidene fluoride-co-hexafluoropropylene)-graft-poly(dopamine methacrylamide) copolymers: A nonlinear dielectric material for high energy density storage

    NASA Astrophysics Data System (ADS)

    Rahimabady, Mojtaba; Qun Xu, Li; Arabnejad, Saeid; Yao, Kui; Lu, Li; Shim, Victor P. W.; Gee Neoh, Koon; Kang, En-Tang

    2013-12-01

    A nonlinear dielectric poly(vinylidene fluoride-co-hexafluoropropylene)-graft-poly(dopamine methacrylamide) [P(VDF-HFP)-g-PDMA] graft copolymer with ultra-high energy density of 33 J/cm3 was obtained by thermally initiated radical graft polymerization. It was observed that the dielectric constant of the graft copolymer films was 63% higher than that of P(VDF-HFP), with a large dielectric breakdown strength (>850 MV/m). Theoretical analyses and experimental measurements showed that the significant improvement in the electric polarization was attributed to the introduction of the highly polarizable hydroxyl groups in the PDMA side chains, and the large breakdown strength arose from the strong adhesion bonding of the catechol-containing graft copolymer to the metal electrode.

  4. Craniofacial Bone Grafting: Wolff's Law Revisited

    PubMed Central

    Oppenheimer, Adam J.; Tong, Lawrence; Buchman, Steven R.

    2008-01-01

    Bone grafts are used for the reconstruction of congenital and acquired deformities of the facial skeleton and, as such, comprise a vital component of the craniofacial surgeon's armamentarium. A thorough understanding of bone graft physiology and the factors that affect graft behavior is therefore essential in developing a more intelligent use of bone grafts in clinical practice. This article presents a review of the basic physiology of bone grafting along with a survey of pertinent concepts and current research. The factors responsible for bone graft survival are emphasized. PMID:22110789

  5. Developments at the graft interface in homo- and hetero-grafts

    PubMed Central

    Clemente Moreno, Maria José; Hevin, Cyril; Ollat, Nathalie; Cookson, Sarah Jane

    2014-01-01

    Gene expression changes induced during graft union formation (the first month after grafting) in grapevine have been studied using whole genome microarrays. The genes differentially expressed between the rootstock and graft interface tissues of homo-grafts (Cabernet Sauvignon (CS) grafted onto CS) were compared at 3 and 28 days after grafting (dag). Graft union formation was associated with the upregulation of genes involved in secondary metabolism, cell wall, wound responses and hormone signaling. These gene expression differences were associated with the accumulation of lignin, cellulose and callose in the callus cells. Superimposed upon this, hetero-grafting between two different grapevine genotypes resulted in the further upregulation of stress and/or defense responses at the graft interface. Here we discuss the limitations of the techniques used to study the developments at the graft interface to date and future research directions to understand graft union formation in plants. PMID:24770337

  6. Saphenous vein forearm grafts and gortex thigh grafts as alternative forms of vascular access.

    PubMed

    Bhandari, S; Wilkinson, A; Sellars, L

    1995-11-01

    To compare the survival and complication rates of saphenous vein forearm grafts and gortex thigh grafts. Retrospective study over a twelve-year period with review of case-notes. Saphenous vein forearm grafts were constructed in 17 males and 12 females, mean age 61 years and gortex thigh grafts in 24 males and 22 females (49 grafts), mean age 49 years. Grafts were the primary form of access in 9 patients in each group. Follow-up was 45.6 and 135.2 patient years on dialysis for forearm grafts and thigh grafts respectively. One-year total survival was 89.4% (89.4% at 2 years and 71.5% at 3 years) and 84.9% (82.3% at 2 years and 70.4% at 3 years) for saphenous vein forearm grafts and gortex thigh grafts respectively. The overall complication rates were 0.22 and 0.61 per patient year on dialysis for saphenous vein forearm grafts and gortex thigh grafts respectively. Thrombosis occurred in 10% and 52%, infection in 0% and 35% and no complications in 62% and 24% of saphenous vein forearm grafts and gortex thigh grafts respectively. Both saphenous vein forearm grafts and gortex thigh grafts can provide satisfactory vascular access. The survival is similar at one year but gortex thigh grafts have a higher complication rate. PMID:8605714

  7. Impaction grafting of the acetabulum with ceramic bone graft substitute

    PubMed Central

    Dacombe, Peter J; Webb, Jason C J; Blom, Ashley W

    2013-01-01

    Background and purpose Loss of bone stock remains a challenge in revision hip surgery. Grafting with allograft is well established, but there are problems with availability, cost, infection, antigenicity, reproducibility, and stability of the created construct. BoneSave is a biphasic porous ceramic consisting of sintered 80% tricalcium phosphate and 20% hydroxyapatite. In vitro and in vivo studies, including its use mixed with allograft, have shown good results in impaction grafting. This is the first reported series of its use alone in impaction grafting of the acetabulum. Methods Methods We conducted a retrospective review of a cohort of 43 consecutive patients undergoing impaction grafting of contained acetabular defects by multiple surgeons at a single centre. All patients received uncemented acetabular components. They were followed up radiographically, together with self-reported satisfaction scale (SAPS), Oxford hip score (OHS), and Short-Form 12 (SF12) health survey. Kaplan-Meier survivorship analysis was performed with revision of the acetabular component, revision of any part of the construct, and reoperation as endpoints. Results The fate of all cases was known. Mean follow-up was 4 years. 5 patients died during follow-up, with their constructs in situ. The survivorship of the acetabular component was 98% (95% CI: 85–100) at 7 years. 1 acetabular component was revised for infection and there was 1 radiographic acetabular failure. The median OHS was 36 (6–48), the median SF12 PCS was 36 (14–57), the median SAPS was 75 (0–100), and the median SF12 MCS was 50 (23–64). The graft material had incorporated in all 3 zones of the acetabulum in 33 out of 37 cases with complete radiographic follow-up. Interpretation Medium-term results show that BoneSave alone is a reliable material for impaction grafting of contained defects in the acetabulum at revision surgery. PMID:23992140

  8. Synthesis and characterization of a novel graft copolymer of partially carboxymethylated guar gum and N-vinylformamide.

    PubMed

    Mishra, Madan Mohan; Mishra, Dinesh Kumar; Mishra, Pushyamitra; Behari, Kunj

    2015-01-22

    Graft copolymer of partially carboxymethylated guar gum (CMGOH) and N-vinylformamide (NVF) was synthesized by free radical polymerization using 2,2-Azobis [2-(2-imadazolin-2-yl) propane] dihydrochloride (AIPH) as initiator. The effect of various reaction parameters such as concentration of NVF, CMGOH, sulphuric acid and AIPH, as well as reaction time and temperature were investigated, and the grafting conditions were optimized. Percent total conversion, % grafting, grafting efficiency (%) and percent add on under different conditions were evaluated and compared. The reaction mechanism for graft copolymerization discussed. Studies on swelling, metal ion uptake and flocculation properties were carried out in aqueous medium and the results obtained are presented and discussed. Both CMGOH and its corresponding graft copolymer samples were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Looking at the reasonable results obtained, the synthesized graft copolymers CMGOH-g-NVF, may be exploited as potential candidates for some industrial important applications as flocculent superabsorbent, and other similar applications. PMID:25439961

  9. Plant grafting: new mechanisms, evolutionary implications.

    PubMed

    Goldschmidt, Eliezer E

    2014-01-01

    Grafting, an old plant propagation practice, is still widely used with fruit trees and in recent decades also with vegetables. Taxonomic proximity is a general prerequisite for successful graft-take and long-term survival of the grafted, composite plant. However, the mechanisms underlying interspecific graft incompatibility are as yet insufficiently understood. Hormonal signals, auxin in particular, are believed to play an important role in the wound healing and vascular regeneration within the graft union zone. Incomplete and convoluted vascular connections impede the vital upward and downward whole plant transfer routes. Long-distance protein, mRNA and small RNA graft-transmissible signals currently emerge as novel mechanisms which regulate nutritional and developmental root/top relations and may play a pivotal role in grafting physiology. Grafting also has significant pathogenic projections. On one hand, stock to scion mechanical contact enables the spread of diseases, even without a complete graft union. But, on the other hand, grafting onto resistant rootstocks serves as a principal tool in the management of fruit tree plagues and vegetable soil-borne diseases. The 'graft hybrid' historic controversy has not yet been resolved. Recent evidence suggests that epigenetic modification of DNA-methylation patterns may account for certain graft-transformation phenomena. Root grafting is a wide spread natural phenomenon; both intraspecific and interspecific root grafts have been recorded. Root grafts have an evolutionary role in the survival of storm-hit forest stands as well as in the spread of devastating diseases. A more fundamental evolutionary role is hinted by recent findings that demonstrate plastid and nuclear genome transfer between distinct Nicotiana species in the graft union zone, within a tissue culture system. This has led to the formation of alloploid cells that, under laboratory conditions, gave rise to a novel, alloploid Nicotiana species, indicating that natural grafts may play a role in plant speciation, under certain circumstances. PMID:25566298

  10. Plant grafting: new mechanisms, evolutionary implications

    PubMed Central

    Goldschmidt, Eliezer E.

    2014-01-01

    Grafting, an old plant propagation practice, is still widely used with fruit trees and in recent decades also with vegetables. Taxonomic proximity is a general prerequisite for successful graft-take and long-term survival of the grafted, composite plant. However, the mechanisms underlying interspecific graft incompatibility are as yet insufficiently understood. Hormonal signals, auxin in particular, are believed to play an important role in the wound healing and vascular regeneration within the graft union zone. Incomplete and convoluted vascular connections impede the vital upward and downward whole plant transfer routes. Long-distance protein, mRNA and small RNA graft-transmissible signals currently emerge as novel mechanisms which regulate nutritional and developmental root/top relations and may play a pivotal role in grafting physiology. Grafting also has significant pathogenic projections. On one hand, stock to scion mechanical contact enables the spread of diseases, even without a complete graft union. But, on the other hand, grafting onto resistant rootstocks serves as a principal tool in the management of fruit tree plagues and vegetable soil-borne diseases. The ‘graft hybrid’ historic controversy has not yet been resolved. Recent evidence suggests that epigenetic modification of DNA-methylation patterns may account for certain graft-transformation phenomena. Root grafting is a wide spread natural phenomenon; both intraspecific and interspecific root grafts have been recorded. Root grafts have an evolutionary role in the survival of storm-hit forest stands as well as in the spread of devastating diseases. A more fundamental evolutionary role is hinted by recent findings that demonstrate plastid and nuclear genome transfer between distinct Nicotiana species in the graft union zone, within a tissue culture system. This has led to the formation of alloploid cells that, under laboratory conditions, gave rise to a novel, alloploid Nicotiana species, indicating that natural grafts may play a role in plant speciation, under certain circumstances. PMID:25566298

  11. Enhancing antibiofouling performance of Polysulfone (PSf) membrane by photo-grafting of capsaicin derivative and acrylic acid

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Sun, Haijing; Gao, Xueli; Gao, Congjie

    2014-10-01

    Biofouling is a critical issue in membrane water and wastewater treatment. Herein, antibiofouling PSf membrane was prepared by UV-assisted graft polymerization of acrylic acid (AA) and a capsaicin derivative, N-(5-methyl-3-tert-butyl-2-hydroxy benzyl) acrylamide (MBHBA), on PSf membrane. AA and MBHBA were used as hydrophilic monomer and antibacterial monomer separately. The membranes were characterized by FTIR-ATR, contact angle, SEM, AFM, cross-flow filtration unit, antifouling and antibacterial measurements. Verification of MBHBA and AA that photo-chemically grafted onto the PSf membrane surface is confirmed by carbonyl stretching vibration at ∼1655 cm-1 and ∼1730 cm-1, separately. The increasing AA concentration accelerates the graft-polymerization of MBHBA and resulted in a more hydrophilic surface. Consequently, antifouling property of the membranes was improved on a large level. The flux recovery rate can achieve 100% during the cyclic test, which may be attributed to the more hydrophilic and smooth surface, as well as the decreased membrane pore size. Most importantly, the presence of AA in graft co-polymer does not affect the antibacterial activity of MBHBA. That may be induced by the increasing chain length and flexibility of the grafted polymer chains.

  12. Types of Coronary Artery Bypass Grafting

    MedlinePlus

    ... best option for you based on your needs. Traditional Coronary Artery Bypass Grafting Traditional CABG is used when at least one major ... Grafting This type of CABG is similar to traditional CABG because the chest bone is opened to ...

  13. Who Needs Coronary Artery Bypass Grafting?

    MedlinePlus

    ... the NHLBI on Twitter. Who Needs Coronary Artery Bypass Grafting? Coronary artery bypass grafting (CABG) is used ... is a test that uses dye and special x rays to show the insides of your coronary arteries. ...

  14. POST CORONARY ARTERY BYPASS GRAFT STUDY (CABG)

    EPA Science Inventory

    Relative effectiveness of moderate versus more aggressive lipid lowering, and of low dose anticoagulation versus placebo, in delaying saphenous vein coronary bypass graft atherosclerosis and preventing occlusion of saphenous grafts of patients with saphenous vein coronary bypass ...

  15. High temperature structural, polymeric foams from high internal emulsion polymerization

    SciTech Connect

    Hoisington, M.A.; Duke, J.R.; Apen, P.G.

    1996-02-01

    In 1982, a high internal phase emulsion (HIPE) polymerization process to manufacture microcellular, polymeric foam systems was patented by Unilever. This patent discloses a polymerization process that occurs in a water-in-oil emulsion in which the water represents at least 76% of the emulsion by volume. The oil phase consists of vinyl monomers such as styrene and acrylates that are crosslinked by divinyl monomers during polymerization. After polymerization and drying to remove the water phase, the result is a crosslinked polymer foam with an open cell microstructure that is homogeneous throughout in terms of morphology, density, and mechanical properties. Since 1982, numerous patents have examined various HIPE polymerized foam processing techniques and applications that include absorbents for body fluids, cleaning materials, and ion exchange systems. All the published HIPE polymerized foams have concentrated on materials for low temperature applications. Copolymerization of styrene with maleic anhydride and N-substituted maleimides to produce heat resistant thermoplastics has been studied extensively. These investigations have shown that styrene will free radically copolymerize with N-substituted maleimides to create an alternating thermoplastic copolymer with a Tg of approximately 200{degrees}C. However, there are many difficulties in attempting the maleimide styrene copolymerization in a HIPE such as lower polymerization temperatures, maleimide solubility difficulties in both styrene and water, and difficulty obtaining a stable HIPE with a styrene/maleimide oil phase. This work describes the preparation of copolymer foams from N-ethylmaleimide and Bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane with styrene based monomers and crosslinking agents.

  16. Recanalization of an Occluded Infrainguinal Vein Graft Complicated by Graft Aneurysm

    SciTech Connect

    Kakani, Nirmal; Travis, Simon; Hancock, John

    2007-11-15

    The technique of subintimal angioplasty has been described for the recanalisation of native vessels after occlusion of infrainguinal vascular bypass grafts. We report a case in which an attempt at such treatment resulted in inadvertent but successful recanalisation of the occluded vein graft instead. This was complicated by graft perforation and subsequent graft aneurysm which was successfully treated with a covered stent.

  17. Organometallic Polymeric Conductors

    NASA Technical Reports Server (NTRS)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

  18. Surface grafting density analysis of high anti-clotting PU-Si-g-P(MPC) films

    NASA Astrophysics Data System (ADS)

    Lu, Chun-Yan; Zhou, Ning-Lin; Xiao, Ying-Hong; Tang, Yi-Da; Jin, Su-Xing; Wu, Yue; Zhang, Jun; Shen, Jian

    2012-02-01

    Well-defined zwitterionic polymer brushes with good blood compatibility were studied, grafted from polyurethane (PU) substrate (PU-Si-g-P(MPC)) by surface-initiated reverse atom transfer radical polymerization (SI-RATRP). We found that the structure of polymer brushes and hence their properties greatly depend on the grafting density. To solve the problems of the normal method for grafting density measurement, i.e., more requirements for qualified and proficient instrument operator, we established an effective and feasible way instead of the conventional method of spectroscopic ellipsometer combined with gel permeation chromatograph (ELM/GPC) to calculate the grafting density of PU-Si-g-P(MPC) films by using a software named ImageJ 1.44e in combination with scanning electronic microscope (SEM) or atomic microscope (AFM). X-ray photoelectron spectroscopy (XPS), SEM and AFM were employed to analyze the surface topography and changes of elements before and after graft modification of the synthetic PU-Si-g-P(MPC) biofilms.

  19. Self-Assembly of Grafted Nanoparticles for Transport Channels in Membranes

    NASA Astrophysics Data System (ADS)

    Bilchak, Connor; Buenning, Ellie; Durning, Christopher; Kumar, Sanat

    2015-03-01

    Polymer membranes have seen increased application for vapor separations, particularly for natural gas processing and purification. The addition of nanoparticles to such membranes has led to conflicting findings; conventional (Maxwell) composite theory predicts the addition of inert filler to hinder membrane transport properties. However, our research using silica nanoparticles grafted with Poly (Methacrylate) has shown these grafted systems to possess permeabilities similar to those of a pure polymer system increasing penetrant solubility without compromising diffusivity. This is counterintuitive to Maxwell theory. We propose that the grafted nanoparticles self-assemble into an ordered crystal lattice containing low-density ``channels'' which facilitate penetrant uptake. Atomic force microscopy and small-angle neutron scattering experiments appear to confirm this theory. Varying polymer grafting density and chain length is also predicted to alter transport properties, allowing for the fabrication of membrane with tunable diffusivity and selectivity. These grafted nanocomposite systems therefore represent a means of creating robust membranes with transport properties similar to those of conventional polymeric films that may be easily adapted for various separations processes. Corresponding author.

  20. Chain Length and Grafting Density Dependent Enhancement in the Hydrolysis of Ester-Linked Polymer Brushes.

    PubMed

    Melzak, Kathryn A; Yu, Kai; Bo, Deng; Kizhakkedathu, Jayachandran N; Toca-Herrera, José L

    2015-06-16

    Poly(N,N-dimethylacrylamide) (PDMA) brushes with different grafting density and chain length were grown from an ester group-containing initiator using surface-initiated polymerization. Hydrolysis of the PDMA chains from the surface was monitored by measuring thickness of the polymer layer by ellipsometry and extension length by atomic force microscopy. It was found that the initial rate of cleavage of one end-tethered PDMA chains was dependent on the grafting density and chain length; the hydrolysis rate was faster for high grafting density brushes and brushes with higher molecular weights. Additionally, the rate of cleavage of polymer chains during a given experiment changed by up to 1 order of magnitude as the reaction progressed, with a distinct transition to a lower rate as the grafting density decreased. Also, polymer chains undergo selective cleavage, with longer chains in a polydisperse brush being preferentially cleaved at one stage of the hydrolysis reaction. We suggest that the enhanced initial hydrolysis rates seen at high grafting densities and high chain lengths are due to mechanical activation of the ester bond connecting the polymer chains to the surface in association with high lateral pressure within the brush. These results have implications for the preparation of polymers brushes, their stability under harsh conditions, and the analysis of polymer brushes from partial hydrolysates. PMID:26010390

  1. Control of Cell Attachment and Spreading on Poly(acrylamide) Brushes with Varied Grafting Density.

    PubMed

    Lilge, Inga; Schönherr, Holger

    2016-01-26

    To achieve spatial control of fibroblast cell attachment and spreading on a biocompatible polymer coating, the effect of poly(acrylamide) (PAAm) brushes with varied grafting density was investigated. The synthesis of the brushes was performed by surface-initiated atom transfer radical polymerization (SI-ATRP). Gold substrates were modified with binary self-assembled monolayers (SAMs) of an initiator and 16-mercaptohexadecanoic acid (MHDA) as an "inert" thiol to initiate the ATRP of AAm. By using different mixtures for the binary SAMs, a series of polymer brushes with varied grafting densities were prepared. The fractional coverage of surface bound initiator was determined by grazing incidence Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and contact angle measurements. A linear relationship between the Br/S ratio determined by XPS and ToF-SIMS versus the fraction of initiator on the surface determined by water contact angle measurements was observed. The varied initiation concentration on the gold substrates yielded PAAm brushes with different thicknesses, indicating a transition from mushroom to brush regimes with increasing grafting density. Thereby we achieved exquisite control of the degree of cell adhesion. Cell attachment experiments with NIH 3T3 fibroblast cells revealed cell spreading on PAAm brushes with low grafting densities (initiator fractional coverage <0.2) as well as a complete passivation by polymer brushes with higher grafting densities. PMID:26771447

  2. Evidence for vertical phase separation in densely grafted, high-molecular-weight poly(N-isopropylacrylamide) brushes in water

    SciTech Connect

    Yim, H.; Kent, M.S.; Satija, S.; Mendez, S.; Balamurugan, S.S.; Balamurugan, S.; Lopez, G.P.

    2005-11-01

    The detailed conformational change of poly(N-isopropylacrylamide) (PNIPAM) brushes at high grafting density in D{sub 2}O was investigated as a function of temperature using neutron reflection. PNIPAM chains were grafted at high surface density from gold and silicon oxide surfaces by atom transfer radical polymerization. Whereas single layer profiles were observed for temperatures below and above the transition region, bilayer profiles were observed for a narrow range of temperatures near the transition. This nonmonotonic change in the concentration profile with temperature is discussed in the context of theoretical models of vertical phase separation within a brush.

  3. Properties of extruded starch-poly(methyl acrylate) graft copolymers prepared from spherulites formed from amylose-oleic acid inclusion complexes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Mixtures of high amylose corn starch and oleic acid were processed by steam jet-cooking, and the dispersions were rapidly cooled to yield amylose-oleic acid inclusion complexes as sub-micron spherulites and spherulite aggregates. Dispersions of these spherulite particles were then graft polymerized ...

  4. Infections in lower extremity vascular grafts.

    PubMed

    Piano, G

    1995-08-01

    No set of rigid guidelines can replace a clinically rational and methodic approach to the patient with an infrainguinal graft infection. Some fundamental principles are common to infrainguinal graft infections that form the basis for selective management: 1. Graft preservation can be attempted when the graft is patent, the anastomosis is intact, and the patient is not septic. 2. Graft excision is mandatory when the patient presents with a thrombosed infected graft, anastomotic or graft hemorrhage, or significant systemic sepsis. 3. Graft preservation can be attempted in both vein and PTFE grafts but is not advised for Dacron grafts. This approach should be tempered by the extent and virulence of the underlying infection, especially when Pseudomonas aeruginosa is the pathologic organism. 4. Delayed hemorrhage and continued systemic sepsis represent early failures of graft preservation and mandate graft excision. 5. Revascularization may be accomplished through the infected bed, but it is generally prudent to proceed with extra-anatomic reconstruction utilizing alternative approaches to inflow and outflow vessels. PMID:7638723

  5. Organosiloxane-grafted natural polymer coatings

    DOEpatents

    Sugama, Toshifumi

    1998-01-01

    A new family of polysaccharide graft polymers are provided as corrosion resistant coatings having antimicrobial properties which are useful on light metals such as aluminum, magnesium, zinc, steel and their alloys. Methods of making the polysaccharide graft polymers are also included. The methods of making the polysaccharide graft polymers involve reacting a polysaccharide source with an antimicrobial agent under conditions of hydrolysis-condensation.

  6. Excimer UV lamp irradiation induced grafting on synthetic polymers

    NASA Astrophysics Data System (ADS)

    Praschak, D.; Bahners, T.; Schollmeyer, E.

    Surface modifications on polyethyleneterephthalate (PET) films following excimer UV lamp irradiation induced grafting were studied. Characteristics of the modifications depending on the conditions during the irradiation were analysed using contact-angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FTIR). Depending on the conditions during the irradiation different surface modifications were obtained, which can generally be classified regarding the hydrophilic or hydrophobic characteristics of the resulting surface. It is shown that not every substance that meets the general demands will be grafted on synthetic polymers using excimer UV radiation. Examples of agents that can simply be grafted onto polymer surfaces and those that undergo further crosslinking, building up thin films are listed. Agents used for grafting on polymers are 1,5-hexadiene, perfluoro-4-methyl-pent-2-ene, polyethyleneglycol 200, monosilane and polyethylene. The transferability of the effects achieved to substrates such as polyparaphenylene terephthalamide or polymetaphenylene isophthalamide is shown.

  7. On-demand degrafting and the study of molecular weight and grafting density of poly(methyl methacrylate) brushes on flat silica substrates.

    PubMed

    Patil, Rohan R; Turgman-Cohen, Salomon; Šrogl, Jiří; Kiserow, Douglas; Genzer, Jan

    2015-03-01

    We report on degrafting of surface-anchored poly(methyl methacrylate) (PMMA) brushes from flat silica-based substrates using tetrabutylammonium fluoride (TBAF) and determining their molecular weight distribution (MWD) using size exclusion chromatography (SEC). The grafted PMMA layer was synthesized using surface-initiated atom transfer radical polymerization (SI-ATRP) of MMA for polymerization times ranging from 6 to 24 h. X-ray photoelectron spectroscopy, ellipsometry, and time-of-flight secondary ion mass spectrometry were employed in tandem to characterize the degrafting process. The SEC eluograms were fit to various polymer distributions, namely Zimm-Schulz, ATRP in continuous stirred tank reactor, Wesslau, Schulz-Flory, and Smith et al. The ATRP model gives the best fit to the experimental data. The dry PMMA brush thickness and the number-average molecular weight (obtained from the MWD) suggest that the grafting density of the PMMA grafts is independent of polymerization time, indicating well-controlled/living growth of MMA. The observed polydispersity index (PDI) was higher than that generally observed in bulk grown polymers under similar conditions, indicating an effect due to chain confinement and crowding. We detect small but noticeable dependence of the polymer brush grafting density on the inhibitor/catalyst ratio. Higher inhibitor/catalyst ratio offers better control with lower early terminations, which results in a small increase in the apparent grafting density of the chains. PMID:25654273

  8. Polymerization of anionic wormlike micelles.

    PubMed

    Zhu, Zhiyuan; González, Yamaira I; Xu, Hangxun; Kaler, Eric W; Liu, Shiyong

    2006-01-31

    Polymerizable anionic wormlike micelles are obtained upon mixing the hydrotropic salt p-toluidine hydrochloride (PTHC) with the reactive anionic surfactant sodium 4-(8-methacryloyloxyoctyl)oxybenzene sulfonate (MOBS). Polymerization captures the cross-sectional radius of the micelles (approximately 2 nm), induces micellar growth, and leads to the formation of a stable single-phase dispersion of wormlike micellar polymers. The unpolymerized and polymerized micelles were characterized using static and dynamic laser light scattering, small-angle neutron scattering, 1H NMR, and stopped-flow light scattering. Stopped-flow light scattering was also used to measure the average lifetime of the unpolymerized wormlike micelles. A comparison of the average lifetime of unpolymerized wormlike micelles with the surfactant monomer propagation rate was used to elucidate the mechanism of polymerization. There is a significant correlation between the ratio of the average lifetime to the monomer propagation rate and the average aggregation number of the polymerized wormlike micelles. PMID:16430253

  9. Admicellar polymerization of precipated silica

    SciTech Connect

    Reynolds, J.L.; Grady, B.P.; Harwell, J.H.

    1996-10-01

    The tendency of a surfactant molecule to adsorb at a solid-liquid interface is the basis for an in situ surface modification process, termed admicellar polymerization. The four-step admicellar polymerization process includes: (1) adsorption of surfactant at the solid-liquid interface, (2) adsolubilization of monomer into the surfactant bilayer, (3) polymerization using free-radical initiators and heat, (4) removal of excess surfactant to expose the polymer modified surface. The process is used to apply polymer to precipitated silica to enhance the compatibility of the silica when added to filled rubber. The adsorption isotherms were first determined for particular surfactant/silica combinations to find the surfactant concentration that would sufficiently adsolubilize the monomer, while remaining below the critical micelle concentration. A series of experiments were then devised for the polymerization reactions in which the surfactant and monomer amounts were varied over three levels to establish the optimal combination.

  10. Integration of RAFT polymerization and click chemistry to fabricate PAMPS modified macroporous polypropylene membrane for protein fouling mitigation.

    PubMed

    Wang, Yun; Wang, Li-Li; He, Xiao-Chun; Zhang, Zi-Jun; Yu, Hai-Yin; Gu, Jia-Shan

    2014-12-01

    A copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC) grafting-to method was used to tether alkyne-terminated poly(2-acrylamido-2-methyl propane sulfonic acid) (alkyne-PAMPS) to the azide functionalized macroporous polypropylene membrane (MPPM-N3). Alkyne-PAMPS was synthesized by the reversible addition-fragmentation chain transfer polymerization (RAFT) of AMPS with an alkyne-terminated trithiocarbonate served as a chain transfer agent. The combination of RAFT polymerization with click chemistry to graft polymer to the surface of polypropylene membrane produced relatively high grafting density and controllable grafting chain length. The structure and composition of the modified and unmodified MPPM surfaces were analyzed by attenuated total reflection-Fourier transform infrared spectroscopy (ATR/FT-IR), X-ray photoelectron spectroscopy (XPS); field emission scanning electron microscopy (FE-SEM) was employed to observe the morphological changes on the membrane surface. The permeation performances were tested by the filtration of protein dispersion. The experimental results show that with the grafting degree going up, the relative flux reduction decreases, while the relative flux recovery ratio increases, and the protein fouling is obviously mitigated by tethering PAMPS to the membrane surface. The modified membranes can be potentially applied for fouling reduction during the filtration of proteins. PMID:25217729

  11. Kinetics of silica polymerization

    SciTech Connect

    Weres, O.; Yee, A.; Tsao, L.

    1980-05-01

    The polymerization of silicic acid in geothermal brine-like aqueous solutions to produce amorphous silica in colloidal form has been studied experimentally and theoretically. A large amount of high quality experimental data has been generated over the temperature rang 23 to 100{sup 0}C. Wide ranges of dissolved silica concentration, pH, and sodium chloride concentration were covered. The catalytic effects of fluoride and the reaction inhibiting effects of aluminum and boron were studied also. Two basic processes have been separately studied: the formation of new colloidal particles by the homogeneous nucleation process and the deposition of dissolved silica on pre-existing colloidal particles. A rigorous theory of the formation of colloidal particles of amorphous silica by homogeneous nucleation was developed. This theory employs the Lothe-Pound formalism, and is embodied in the computer code SILNUC which quantitatively models the homogeneous nucleation and growth of colloidal silica particles in more than enough detail for practical application. The theory and code were extensively used in planning the experimental work and analyzing the data produced. The code is now complete and running in its final form. It is capable of reproducing most of the experimental results to within experimental error. It is also capable of extrapolation to experimentally inaccessible conditions, i.e., high temperatures, rapidly varying temperature and pH, etc.

  12. Graft-vs-host disease.

    PubMed

    Tran, Kathleen; Kaplan, Jennifer; Kamino, Hideko; Latkowski, Jo-Ann

    2013-12-01

    We present a case of chronic graft-versus-host disease in a 61-year-old woman with a history of B-cell chronic lymphocytic leukemia that was treated with an allogeneic bone marrow transplant from an unrelated donor. The patient initially presented with erythematous patches on the trunk and extremities that evolved into reticulated, hyperpigmented patches and lichenified plaques. PMID:24365001

  13. Polyether-polyester graft copolymer

    NASA Technical Reports Server (NTRS)

    Bell, Vernon L. (Inventor)

    1987-01-01

    Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

  14. In situ grafting silica nanoparticles reinforced nanocomposite hydrogels.

    PubMed

    Yang, Jun; Han, Chun-Rui; Duan, Jiu-Fang; Xu, Feng; Sun, Run-Cang

    2013-11-21

    Highly flexible nanocomposite hydrogels were prepared by using silica nanoparticles (SNPs) as fillers and multi-functional cross-links to graft hydrophilic poly(acrylic acid) (PAA) by free radical polymerization from an aqueous solution. The SNPs were collected by neighboring polymer chains and dispersed uniformly within a PAA matrix. The mechanical properties of the nanocomposite hydrogels were tailored by the concentration of SNPs according to the percolation model. It was proposed that covalent bonds of adsorbed chains on the filler surface resulted in the formation of a shell of an immobilized glassy layer and trapped entanglements, where the glassy polymer layer greatly enhanced the elastic modulus and the release of trapped entanglements at deformation contributed to the viscoelastic properties. PMID:24089085

  15. Gels from soft hairy nanoparticles in polymeric matrices

    NASA Astrophysics Data System (ADS)

    Vlassopoulos, Dimitris

    2013-03-01

    Hairy particles represent a huge class of soft colloids with tunable interactions and properties. Advances in synthetic chemistry have enabled obtaining well-characterized such systems for specific needs. In this talk we present two model hairy soft particles with diameters of the order of tens of nanometers, star polymers and polymerically grafted spherical particles. In particular, we discuss design strategies for dispersing them in polymeric matrices and eventually creating and breaking gels. Control parameters are the matrix molar mass, the grafting density (or functionality) and the size of the grafts (or arms). The linear viscoelastic properties and slow time evolution of the gels are examined in view of the existing knowledge from colloidal gels consisting of micron-sized particles, and compared. In the case of stars we start from a concentrated glassy suspension in molecular solvent and add homopolymer at increasing concentration, and as a result of the induced osmotic pressure the stars shrink and a depletion gel is formed. For the grafted colloidal particles, they are added at low concentration to a polymer matrix, and it has been shown that under certain conditions the anisotropy of interactions gives rise to network formation. We then focus on the nonlinear rheological response and in particular the effect of shear flow in inducing a solid to liquid transition. Our studies show that the yielding process is gradual and shares many common features with that of flocculated colloidal suspensions, irrespectively of the shape of the building block of the gel. Whereas shear can melt such a gel, it cannot break it into its constituent blocks and hence fully disperse the hairy nanoparticles. On the other hand, the hairy particles are intrinsically hybrid. We show how this important feature is reflected on the heating of the gels. In that case, the mismatch of thermal expansion coefficients of core and shell appears to play a role on the particle response as it imposes and internal strain on the particle, which in turn changes the shell conformation and under some conditions can lead to thermal melting of the gel. These alternative avenues for manipulating the gel-to-liquid transition have potential implications in directing the properties of hairy nanoparticles and their assemblies in viscoelastic matrices. Parts of this work reflect collaboration with D. Truzzolillo (FORTH), J. F. Moll and S. K.Kumar (Columbia). R. H. Colby (Penn State), M. Gauthier (Waterloo) and B. C. Benicewicz (Univ. South Carolina).

  16. Ethyl cellulose amphiphilic graft copolymers with LCST-UCST transition: Opposite self-assembly behavior, hydrophilic-hydrophobic surface and tunable crystalline morphologies.

    PubMed

    Yuan, Hua; Chi, Hai; Yuan, Weizhong

    2016-08-20

    Novel and well-defined graft copolymer with block copolymer side chain, ethyl cellulose-graft-(poly(ε-caprolactone)-block-poly(N,N-dimethylaminoethylmeth acrylate)) (EC-g-(PCL-b-PDMAEMA)) with a lower critical solution temperature (LCST) was successfully synthesized via the combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). EC-g-(PCL-b-PDMAEMA) copolymers with various PCL-b-PDMAEMA block lengths were obtained by adjusting the molar ratios of the N,N-dimethylaminoethyl methacrylate monomer to ε-caprolactone. The EC-g-(PCL-b-PDMAPS) with an upper critical solution temperature (UCST) was obtained via facile quaternization reaction of PDMAEMA with 1,3-propane sultone. EC-g-(PCL-b-PDMAEMA) and EC-g-(PCL-b-PDMAPS) micelle solutions showed opposite thermoresponsiviness and hydrophilic-hydrophobic surface. Moreover, the tunable crystalline morphologies could be obtained from these graft copolymers through changing the polymer structure and PDMAEMA contents. PMID:27178932

  17. Vascular grafting strategies in coronary intervention

    NASA Astrophysics Data System (ADS)

    Knight, Darryl; Gillies, Elizabeth; Mequanint, Kibret

    2014-06-01

    With the growing need for coronary revascularizations globally, several strategies to restore blood flow to the heart have been explored. Bypassing the atherosclerotic coronary arteries with autologous grafts, synthetic prostheses and tissue-engineered vascular grafts continue to be evaluated in search of a readily available vascular graft with clinically acceptable outcomes. The development of such a vascular graft including tissue engineering approaches both in situ and in vitro is herein reviewed, facilitating a detailed comparison on the role of seeded cells in vascular graft patency.

  18. Development of ceramic-supported polymeric membranes for filtration of oil emulsions

    NASA Astrophysics Data System (ADS)

    Castro, Robert P.

    Hybrid ceramic-polymeric membranes have been constructed by growing of covalently-bondedpolyvinylpyrrolidone(PVP) chains from the surface of porous inorganic supports via a graft polymerization process. The ability to manipulate the distribution of grafted polymer on the surface has been achieved through the control of the surface density of chain anchoring sites (vinyl silane molecules). The application of the modification procedure to both silica and alpha-alumina surfaces has been investigated. Resultant Ceramic-Supported Polymeric (CSP) membranes can now be produced with variable surface density and length of the terminally anchored polymer chains. Hydraulic permeability measurements were conducted to demonstrate the effect of this variation in grafted chain density and length on the water permeability of the CSP membranes. Similar measurements with a range of polar and non-polar organic solvents and both unmodified and modified membranes suggested that the permeability of the modified membrane is determined by the chemistry and configuration of the terminally anchored polymer chains. This has been attributed to the fact that the swelling (degree of extension) of the polymer brush layer increases as the solvent power increases, resulting in a decrease in the pore radius and the permeability. The separation performance of these CSP membranes have been evaluated for the cross-flow filtration of oil emulsions. For tubular silica-PVP membranes, a reduction in the TOC concentration of the permeate stream was observed with operation in the fully developed turbulent flow regime. It is hypothesized that this behavior is attributed to the ability of the grafted chains to inhibit penetration of cake layer into the pore structure from the normal component of the velocity vector.

  19. Polymeric materials for neovascularization

    NASA Astrophysics Data System (ADS)

    DeVolder, Ross John

    Revascularization therapies have emerged as a promising strategy to treat various acute and chronic wounds, cardiovascular diseases, and tissue defects. It is common to either administer proangiogenic growth factors, such as vascular endothelial growth factor (VEGF), or transplant cells that endogenously express multiple proangiogenic factors. Additionally, these strategies utilize a wide variety of polymeric systems, including hydrogels and biodegradable plastics, to deliver proangiogenic factors in a sophisticated manner to maintain a sustained proangiogenic environment. Despite some impressive results in rebuilding vascular networks, it is still a challenging task to engineer mature and functional neovessels in target tissues, because of the increasing complexities involved with neovascularization applications. To resolve these challenges, this work aims to design a wide variety of proangiogenic biomaterial systems with tunable properties used for neovascularization therapies. This thesis describes the design of several biomaterial systems used for the delivery of proangiogenic factors in neovascularization therapies, including: an electrospun/electrosprayed biodegradable plastic patch used for directional blood vessel growth (Chapter 2), an alginate-g-pyrrole hydrogel system that biochemically stimulates cellular endogenous proangiogenic factor expression (Chapter 3), an enzyme-catalyzed alginate-g-pyrrole hydrogel system for VEGF delivery (Chapter 4), an enzyme-activated alginate-g-pyrrole hydrogel system with systematically controllable electrical and mechanical properties (Chapter 5), and an alginate-g-pyrrole hydrogel that enables the decoupled control of electrical conductivity and mechanical rigidity and is use to electrically stimulate cellular endogenous proangiogenic factor expression (Chapter 6). Overall, the biomaterial systems developed in this thesis will be broadly useful for improving the quality of a wide array of molecular and cellular based revascularization therapies.

  20. Renal graft irradiation in acute rejection

    SciTech Connect

    Pilepich, M.V.; Sicard, G.A.; Breaux, S.R.; Etheredge, E.E.; Blum, J.; Anderson, C.B.

    1983-03-01

    To evaluate the effect of graft irradiation in the treatment of acute rejection of renal transplants, a randomized study was conducted from 1978 to 1981. Patients with acute rejection were given standard medical management in the form of intravenous methylprednisolone, and were chosen randomly to receive either graft irradiation (175 rads every other day, to a total of 525 rads) or simulated (sham) irradiation. Eighty-three rejections occurring in 64 grafts were randomized to the protocol. Rejection reversal was recorded in 84.5% of control grafts and 75% of the irradiated grafts. Recurrent rejections were more frequent and graft survival was significantly lower in the irradiated group (22%) than in the control group (54%). Graft irradiation does not appear to be beneficial in the treatment of acute rejection of renal transplants when used in conjunction with high-dose steroids.

  1. High-energy radiation and polymers: A review of commercial processes and emerging applications

    NASA Astrophysics Data System (ADS)

    Clough, R. L.

    2001-12-01

    Ionizing radiation has been found to be widely applicable in modifying the structure and properties of polymers, and can be used to tailor the performance of either bulk materials or surfaces. Fifty years of research in polymer radiation chemistry has led to numerous applications of commercial and economic importance, and work remains active in the application of radiation to practical uses involving polymeric materials. This paper provides a survey of radiation-processing methods of industrial interest, ranging from technologies already commercially well established, through innovations in the active R&D stage which show exceptional promise for future commercial use. Radiation-processing technologies are discussed under the following categories: cross-linking of plastics and rubbers, curing of coatings and inks, heat-shrink products, fiber-matrix composites, chain-scission for processing control, surface modification, grafting, hydrogels, sterilization, natural product enhancement, plastics recycling, ceramic precursors, electronic property materials, ion-track membranes and lithography for microdevice production. In addition to new technological innovations utilizing conventional gamma and e-beam sources, a number of promising new applications make use of novel radiation types which include ion beams (heavy ions, light ions, highly focused microscopic beams and high-intensity pulses), soft X-rays which are focused, coherent X-rays (from a synchrotron) and e-beams which undergo scattering to generate patterns.

  2. Aqueous-Based Initiator Attachment and ATRP Grafting of Polymer Brushes from Poly(methyl methacrylate) Substrates

    PubMed Central

    Balamurugan, Sreelatha S.; Subramanian, Balamurugan; Bolivar, Jowell G.; McCarley, Robin L.

    2012-01-01

    Many polymers, such as PMMA, are very susceptible to swelling or dissolution by organic solvents. Growing covalently attached polymer brushes from these surfaces by ATRP is challenging because of the typical requirement of organic solvent for initiator immobilization. We report an unprecedented, aqueous-based route to graft poly(N-isopropylacrylamide), PNIPAAm, from poly(methyl methacrylate), PMMA, surfaces by atom-transfer radical polymerization (ATRP), wherein the underlying PMMA is unaffected. Successful attachment of the ATRP initiator, N-hydroxysuccinimidyl-2-bromo-2-methylpropionate, on amine-bearing PMMA surfaces was confirmed by XPS. From this surface-immobilized initiator, thermoresponsive PNIPAAm brushes were grown by aqueous ATRP to yield optically transparent PNIPAAm-grafted PMMA surfaces. This procedure is valuable, as it can be applied for the aqueous-based covalent attachment of ATRP initiator on any amine-functionalized surface, with subsequent polymerization of a variety of monomers. PMID:22967226

  3. Photoluminescent silicon nanocrystal-polymer hybrid materials via surface initiated reversible addition-fragmentation chain transfer (RAFT) polymerization.

    PubMed

    Höhlein, Ignaz M D; Werz, Patrick D L; Veinot, Jonathan G C; Rieger, Bernhard

    2015-05-01

    Silicon-polymer core-shell hybrid materials are obtained via surface initiated reversible addition-fragmentation chain transfer (RAFT) polymerization from photoluminescent silicon nanocrystals (SiNCs). Polymer grafted SiNCs and free polymers in solution are separated using ultracentrifugation. The polymerization on the surface proceeds in a living manner which is confirmed via GPC, DLS and TGA measurements. This method was applied to various other monomers. The obtained materials all show bright red photoluminescence originating from the SiNC core. PMID:25850065

  4. Photoluminescent silicon nanocrystal-polymer hybrid materials via surface initiated reversible addition-fragmentation chain transfer (RAFT) polymerization

    NASA Astrophysics Data System (ADS)

    Höhlein, Ignaz M. D.; Werz, Patrick D. L.; Veinot, Jonathan G. C.; Rieger, Bernhard

    2015-04-01

    Silicon-polymer core-shell hybrid materials are obtained via surface initiated reversible addition-fragmentation chain transfer (RAFT) polymerization from photoluminescent silicon nanocrystals (SiNCs). Polymer grafted SiNCs and free polymers in solution are separated using ultracentrifugation. The polymerization on the surface proceeds in a living manner which is confirmed via GPC, DLS and TGA measurements. This method was applied to various other monomers. The obtained materials all show bright red photoluminescence originating from the SiNC core.

  5. Model For Bending Actuators That Use Electrostrictive Graft Elastomers

    NASA Technical Reports Server (NTRS)

    Costen, Robert C.; Su, Ji; Harrison, Joycelyn S.

    2001-01-01

    Recently, it was reported that an electrostrictive graft elastomer exhibits large electric field-induced strain (4%). Combined with its high mechanical modulus, the elastomer can offer very promising electromechanical properties, in terms of output mechanical energy density, for an electroactive polymeric material. Therefore, it has been considered as one of the candidates that can be used in high performance, low mass actuation devices in many aerospace applications. Various bilayer- based bending actuators have been designed and fabricated. An analytic model based on beam theory in the strength of materials has been derived for the transverse deflection, or curvature, and the longitudinal strain of the bi-layer beam. The curvature and strain are functions of the applied voltage and the thickness, width, and Young s modulus of the active and passive layers. The model can be used to optimize the performance of electrostrictive graft elastomer-based actuators to meet the requirements of various applications. In this presentation, optimization and sensitivity studies are applied to the bending performance of such actuators.

  6. RAFT "grafting-through" approach to surface-anchored polymers: Electrodeposition of an electroactive methacrylate monomer.

    PubMed

    Grande, C D; Tria, M C; Felipe, M J; Zuluaga, F; Advincula, R

    2011-02-01

    The synthesis of homopolymer and diblock copolymers on surfaces was demonstrated using electrodeposition of a methacrylate-functionalized carbazole dendron and subsequent reversible addition-fragmentation chain transfer (RAFT) "grafting-through" polymerization. First, the anodically electroactive carbazole dendron with methacrylate moiety (G1CzMA) was electrodeposited over a conducting surface (i.e. gold or indium tin oxide (ITO)) using cyclic voltammetry (CV). The electrodeposition process formed a crosslinked layer of carbazole units bearing exposed methacrylate moieties. This film was then used as the surface for RAFT polymerization process of methyl methacrylate (MMA), styrene (S), and tert-butyl acrylate (TBA) in the presence of a free RAFT agent and a free radical initiator, resulting in grafted polymer chains. The molecular weights and the polydispersity indices (PDI) of the sacrificial polymers were determined by gel permeation chromatography (GPC). The stages of surface modification were investigated using X-ray photoelectron spectroscopy (XPS), ellipsometry, and atomic force microscopy (AFM) to confirm the surface composition, thickness, and film morphology, respectively. UV-Vis spectroscopy also confirmed the formation of an electro-optically active crosslinked carbazole film with a [Formula: see text] - [Formula: see text] absorption band from 450-650nm. Static water contact angle measurements confirmed the changes in surface energy of the ultrathin films with each modification step. The controlled polymer growth from the conducting polymer-modified surface suggests the viability of combining electrodeposition and grafting-through approach to form functional polymer ultrathin films. PMID:21337014

  7. Chemical and Nanomechanical Analysis of Rice Husk Modified by ATRP-Grafted Oligomer

    PubMed Central

    Morsi, Samir M.; Pakzad, Anahita; Amin, Amal; Yassar, Reza S.; Heiden, Patricia A.

    2013-01-01

    Rice husk (RH), an abundant agricultural residue, was reacted with 2-bromoisobutyryl bromide, to convert it to a heterogeneous polyfunctional macroinitiator for Atom Transfer Radical Polymerization (ATRP). The number of active sites placed on the RH surface was small, but they were ATRP active. Non-polar methyl methacrylate (MMA) and polar acrylonitrile (AN) were polymerized from the RH, and a sequential monomer addition was used to prepare an amphiphilic PMMA-b-PAN copolymer on RH surface. FTIR qualitatively confirmed the grafting. Gravimetric and XPS analysis of the different RH surface compositions indicated thin layers of oligomeric PMMA, PAN, and PMMA-b-PAN. The modified surfaces were mapped by nanomechanical AFM to measure surface roughness, and adhesion and moduli using the Derjaguin-Muller-Toropov model. RH grafted with MMA possessed a roughness value of 7.92, and a hard and weakly adhering surface (13.1 GPa and 16.7 nN respectively) while RH grafted with AN yielded a roughness value of 29 with hardness and adhesion values of 4.0 GPa and 23.5 nN. The PMMA-b-PAN modification afforded a surface with a roughness value of 51.5 nm, with hardness and adhesion values of 3.0 GPa and .75.3 nN. PMID:21565356

  8. Amphiphilic Graft Copolymer Nanospheres: From Colloidal Self-Assembly to CO2 Capture Membranes.

    PubMed

    Jeon, Harim; Kim, Dong Jun; Park, Min Su; Ryu, Du Yeol; Kim, Jong Hak

    2016-04-13

    Colloidal nanosphere self-assembly effectively generates ordered nanostructures, prompting tremendous interest in many applications such as photonic crystals and templates for inverse opal fabrication. Here we report the self-assembly of low-cost, graft copolymer nanospheres for CO2 capture membranes. Specifically, poly(dimethylsiloxane)-graft-poly(4-vinylpyridine) (PDMS-g-P4VP) is synthesized via one-pot, free radical dispersion polymerization to give discrete monodisperse nanospheres. These nanospheres comprise a surface-anchored highly permeable PDMS layer and internal CO2-philic P4VP spherical core. Their diameter is controllable below the submicrometer range by varying grafting ratios. The colloidal dispersion forms a long-range, close-packed hexagonal array on a substrate by inclined deposition and convective assembly. The array shows dispersion medium-dependent packing characteristics. A thermodynamic correlation is determined using different solvents to obtain stable PDMS-g-P4VP dispersions and interpreted in terms of Flory-Huggins interaction parameter. As a proof-of-concept, the implementation of these nanospheres into membranes simultaneously enhances the CO2 permeability and CO2/N2 selectivity of PDMS-based transport matrixes. Upon physical aging of the solution, the CO2/N2 selectivity is improved up to 26, one of the highest values for highly permeable PDMS-based polymeric membranes. PMID:27004536

  9. Grafting Strategy to Develop Single Site Titanium on an Amorphous Silica Surface

    SciTech Connect

    Capel-Sanchez, M.; Blanco-Brieva, G; Campos-Martin, J; de Frutos, M; Wen, W; Rodriguez, J; Fierro, J

    2009-01-01

    Titanium/silica systems were prepared by grafting a titanium alkoxide (titanium isopropoxide and titanium (triethanolaminate) isopropoxide) precursor onto amorphous silica. The grafting process, which consisted of the hydrolysis of the Ti precursor by the hydroxyl groups on the silica surface, yielded samples containing Ti-loadings of 1-1.6 wt %. The as synthesized and calcined TiO2-SiO2 samples were characterized by UV-vis, FTIR, XPS, and XANES spectroscopic techniques. These systems were tested in the liquid-phase epoxidation of oct-1-ene with hydrogen peroxide reaction. Spectroscopic data indicated that titanium anchoring takes place by reaction between the alkoxide precursor and surface OH groups of the silica substrate. The nature of surface titanium species generated by chemical grafting depends largely on the titanium precursor employed. Thus, the titanium isopropoxide precursor yields tetrahedrally coordinated polymeric titanium species, which give rise to a low-efficiency catalyst. However, if an atrane precursor (titanium (triethanolaminate) isopropoxide) is employed, isolated titanium species are obtained. The fact that these species remain isolated even after calcination is due to the protective effect of the triethanolaminate ligand that avoids titanium polymerization. These differences in the titanium environment have a pivotal role in the performance of these systems in the epoxidation of alkenes with hydrogen peroxide.

  10. Silver nanoparticle based antibacterial methacrylate hydrogels potential for bone graft applications

    PubMed Central

    González-Sánchez, M. Isabel; Perni, Stefano; Tommasi, Giacomo; Morris, Nathanael Glyn; Hawkins, Karl; López-Cabarcos, Enrique; Prokopovich, Polina

    2015-01-01

    Infections are frequent and very undesired occurrences after orthopedic procedures; furthermore, the growing concern caused by the rise in antibiotic resistance is progressively dwindling the efficacy of such drugs. Artificial bone graft materials could solve some of the problems associated with the gold standard use of natural bone graft such as limited bone material, pain at the donor site and rejections if donor tissue is used. We have previously described new acrylate base nanocomposite hydrogels as bone graft materials. In the present paper, we describe the integration of silver nanoparticles in the polymeric mineralized biomaterial to provide non-antibiotic antibacterial activity against Staphylococcus epidermidis and Methicillin-resistant Staphylococcus aureus. Two different crosslinking degrees were tested and the silver nanoparticles were integrated into the composite matrix by means of three different methods: entrapment in the polymeric hydrogel before the mineralization; diffusion during the process of calcium phosphate crystallization and adsorption post-mineralization. The latter being generally the most effective method of encapsulation; however, the adsorption of silver nanoparticles inside the pores of the biomaterial led to a decreasing antibacterial activity for adsorption time longer than 2 days. PMID:25746278

  11. Enhanced Wettability Changes by Synergistic Effect of Micro/Nanoimprinted Substrates and Grafted Thermoresponsive Polymer Brushes.

    PubMed

    Nagase, Kenichi; Onuma, Takahiro; Yamato, Masayuki; Takeda, Naoya; Okano, Teruo

    2015-11-01

    Thermoresponsive polymer brushes are grafted on micro/nanostructured polymer substrates as new intelligent interfaces that synergistically enhance wettability changes in response to external temperature stimuli. Thermoplastic poly(styrene-co-4-vinylbenzyl chloride) [P(St-co-VBC)] is synthesized using radical polymerization and spin-coated on a glass substrate. Micro/nanopillar and hole patterns are imprinted on the P(St-co-VBC) layer using thermal nanoimprint lithography. Poly(N-isopropylacrylamide) (PIPAAm) brushes are grafted on the micro/nanostructured P(St-co-VBC) layer through surface-initiated atom-transfer radical polymerization using 4-vinylbenzyl chloride as the initiator. The imprinted micro/nanostructures and grafted PIPAAm brush chain lengths affect the surface wettability. Combinations of nanopillars or nanoholes (diameter 500 nm) and longer PIPAAm brushes enhance hydrophobic/hydrophilic changes in response to temperature changes, compared with the flat substrate. The thermoresponsive hydrophobic/hydrophilic transition is synergistically enhanced by the nanostructured surface changing from Cassie-Baxter to Wenzel states. This PIPAAm-brush-modified micro/nanostructured P(St-co-VBC) is a new intelligent interface that effectively changes wettability in response to external temperature changes. PMID:26375171

  12. Aortic stent-grafts: Endoleak surveillance.

    PubMed

    Cassagnes, L; Pérignon, R; Amokrane, F; Petermann, A; Bécaud, T; Saint-Lebes, B; Chabrot, P; Rousseau, H; Boyer, L

    2016-01-01

    Endoleaks have been referred to as the "Achilles heel" of endovascular aortic aneurysm repair (EVAR) and are the most common complication of this procedure. An endoleak can maintain a high systemic blood pressure within the aneurysm sac, potentially leading to rupture. Follow-up is therefore mandatory to detect and classify possible endoleaks. Computed tomography (CT) remains the gold standard for follow-up, but provides no hemodynamic information on endoleaks and has the disadvantages of exposing patients to iodine contrast and X-ray radiation. Exposure to radiation could be reduced in various ways, by simplifying the triphasic protocol using dual-energy CT imaging, limiting the amount of radiation per slice using iterative reconstruction, and reducing the follow-up schedule that could be altered to include non-ionizing radiation imaging techniques. Contrast-enhanced ultrasound (CEUS) is an interesting alternative to CT, as is magnetic resonance (MR) imaging that can be used as an alternative or for complementary imaging. Long-term follow-up schedules are currently based on repeated CT. However, more recently alternative follow-up protocols have been proposed for patients with no endoleaks nor increase in aneurysmal sac size. These new protocols consist of CT imaging at 1month and 1year after treatment, subsequently followed by CEUS. Nevertheless, the mechanical structure of the stent-graft must still be verified by CT. The use of patient-specific risk-adjusted follow-up protocols, based on preoperative imaging and the first postoperative results, is gradually becoming more and more widespread. PMID:26254711

  13. Antifungal activity, biofilm-controlling effect, and biocompatibility of poly(N-vinyl-2-pyrrolidinone)-grafted denture materials.

    PubMed

    Sun, Xinbo; Cao, Zhengbing; Yeh, Chih-Ko; Sun, Yuyu

    2013-10-01

    Colonization and biofilm-formation of Candida species on denture surfaces cause Candida-associated denture stomatitis (CADS), a common, recurring disease affecting up to 67% of denture wearers. We developed poly(N-vinyl-2-pyrrolidinone)-grafted denture materials that can be repeatedly recharged with various antifungal drugs to achieve long-term antifungal and biofilm-controlling effects. The monomer, N-vinyl-2-pyrrolidinone (NVP), was grafted onto poly(methyl methacrylate) denture resins through plasma-initiated grafting polymerization. The physical properties and biocompatibility of the resulting resins were not negatively affected by the presence of up to 7.92% of grafted poly (N-vinyl-2-pyrrolidinone) (PNVP). Miconazole and chlorhexidine digluconate (CD) were used as model antifungal drugs. PNVP grafting significantly increased the drug absorption capability of the resulting denture materials. Further, the new materials showed sustained drug release and provided antifungal effects for weeks (in the case of CD) to months (in the case of miconazole). The drug-depleted resins could be recharged with the same or a different class of antifungal drug to further extend antifungal duration. If needed, drugs on the PNVP-grafted denture materials could be "washed out" (quenched) by treating with PNVP aqueous solutions to stop drug release. These results point to great potentials of the new materials in controlling biofilm-formation in a wide range of device-related applications. PMID:23708753

  14. Antifungal activity, biofilm-controlling effect, and biocompatibility of poly(N-vinyl-2-pyrrolidinone)-grafted denture materials

    PubMed Central

    Sun, Xinbo; Cao, Zhengbing; Yeh, Chih-Ko; Sun, Yuyu

    2013-01-01

    Colonization and biofilm-formation of Candida species on denture surfaces cause Candida-associated denture stomatitis (CADS), a common, recurring disease affecting up to 67% of denture wearers. We developed poly(N-vinyl-2-pyrrolidinone)-grafted denture materials that can be repeatedly recharged with various antifungal drugs to achieve long-term antifungal and biofilm-controlling effects. The monomer, N-vinyl-2-pyrrolidinone (NVP), was grafted onto poly(methyl methacrylate) denture resins through plasma-initiated grafting polymerization. The physical properties and biocompatibility of the resulting resins were not negatively affected by the presence of up to 7.92% of grafted poly (N-vinyl-2-pyrrolidinone) (PNVP). Miconazole and chlorhexidine digluconate (CD) were used as model antifungal drugs. PNVP grafting significantly increased the drug absorption capability of the resulting denture materials. Further, the new materials showed sustained drug release and provided antifungal effects for weeks (in the case of CD) to months (in the case of miconazole). The drug-depleted resins could be recharged with the same or a different class of antifungal drug to further extend antifungal duration. If needed, drugs on the PNVP-grafted denture materials could be “washed out” (quenched) by treating with PNVP aqueous solutions to stop drug release. These results point to great potentials of the new materials in controlling biofilm-formation in a wide range of device-related applications. PMID:23708753

  15. Multifunctional network-structured film coating for woven and knitted polyethylene terephthalate against cardiovascular graft-associated infections.

    PubMed

    Al Meslmani, Bassam M; Mahmoud, Gihan F; Sommer, Frank O; Lohoff, Michael D; Bakowsky, Udo

    2015-05-15

    Multifunctional network-structured polymeric coat for woven and knitted forms of crimped polyethylene terephthalate PET graft was developed to limit graft-associated infections. A newly synthesized antibacterial sulfadimethoxine polyhexylene adipate-b-methoxy polyethylene oxide (SD-PHA-b-MPEO) di-block copolymer was employed. Our figures of merit revealed that the formed coat showed a porous topographic architecture which manifested paramount properties, mostly bacterial anti-adhesion efficiency and biocompatibility with host cells. Compared to untreated grafts, the coat presented marked reduction of adhered Gram-positive Staphylococcus epidermidis previously isolated from a patient's vein catheter by 2.6 and 2.3 folds for woven and knitted grafts, respectively. Similarly, bacterial anti-adhesion effect was observed for Staphylococcus aureus by 2.3 and 2.4 folds, and by 2.9 and 2.7 folds for Gram-negative Escherichia coli for woven and knitted grafts, respectively. Additionally, adhesion and growth characteristics of L929 cells on the modified grafts revealed no significant effect on the biocompatibility. In conclusion, coating of PET with (SD-PHA-b-MPEO) is a versatile approach offers the desired bacterial anti-adhesion effect and host biocompatibility. PMID:25796119

  16. Radially and axially graded multizonal bone graft substitutes targeting critical-sized bone defects from polycaprolactone/hydroxyapatite/tricalcium phosphate.

    PubMed

    Ergun, Asli; Yu, Xiaojun; Valdevit, Antonio; Ritter, Arthur; Kalyon, Dilhan M

    2012-12-01

    Repair and regeneration of critical sized defects via the utilization of polymeric bone graft substitutes are challenges. Here, we introduce radially and axially graded multizonal bone graft substitutes fabricated from polycaprolactone (PCL), and PCL biocomposites with osteoconductive particles, that is, hydroxyapatite (HA), and β-tricalcium phosphate (TCP). The novel bone graft substitutes should provide a greater degree of freedom to the orthopedic surgeon especially for repair of critically sized bone defects. The modulus of the graft substitute could be tailored in the axial direction upon the systematic variation of the HA/TCP concentration, while in the radial direction the bone graft substitute consisted of an outer layer with high stiffness, encapsulating a softer core with greater porosity. The biocompatibility of the bone graft substitutes was investigated using in vitro culturing of human bone marrow-derived stromal cells followed by the analysis of cell proliferation and differentiation rates. The characterization of the tissue constructs included the enzymatic alkaline phosphates (ALP) activity, microcomputed tomography imaging, and polymerase chain reaction analysis involving the expressions of bone markers, that is, Runx2, ALP, collagen type I, osteopontin, and osteocalcin, overall demonstrating the differentiation of bone marrow derived stem cells (BMSCs) via osteogenic lineage and formation of mineralized bone tissue. PMID:22764839

  17. Radially and Axially Graded Multizonal Bone Graft Substitutes Targeting Critical-Sized Bone Defects from Polycaprolactone/Hydroxyapatite/Tricalcium Phosphate

    PubMed Central

    Ergun, Asli; Yu, Xiaojun; Valdevit, Antonio; Ritter, Arthur

    2012-01-01

    Repair and regeneration of critical sized defects via the utilization of polymeric bone graft substitutes are challenges. Here, we introduce radially and axially graded multizonal bone graft substitutes fabricated from polycaprolactone (PCL), and PCL biocomposites with osteoconductive particles, that is, hydroxyapatite (HA), and β-tricalcium phosphate (TCP). The novel bone graft substitutes should provide a greater degree of freedom to the orthopedic surgeon especially for repair of critically sized bone defects. The modulus of the graft substitute could be tailored in the axial direction upon the systematic variation of the HA/TCP concentration, while in the radial direction the bone graft substitute consisted of an outer layer with high stiffness, encapsulating a softer core with greater porosity. The biocompatibility of the bone graft substitutes was investigated using in vitro culturing of human bone marrow-derived stromal cells followed by the analysis of cell proliferation and differentiation rates. The characterization of the tissue constructs included the enzymatic alkaline phosphates (ALP) activity, microcomputed tomography imaging, and polymerase chain reaction analysis involving the expressions of bone markers, that is, Runx2, ALP, collagen type I, osteopontin, and osteocalcin, overall demonstrating the differentiation of bone marrow derived stem cells (BMSCs) via osteogenic lineage and formation of mineralized bone tissue. PMID:22764839

  18. Immobilization of quaternary ammonium salts on grafting particle polystyrene/SiO 2 and preliminary study of application performance

    NASA Astrophysics Data System (ADS)

    Gao, Baojiao; Qi, Changsheng; Liu, Qing

    2008-04-01

    Polystyrene (PSt) was grafted on the surface of silica gel particles in the manner of "grafting from" in a solution polymerization system, and grafting particles PSt/SiO 2 was obtained. The chloromethylation reaction of the grafted polystyrene was performed using a novel chloromethylation reagent, 1,4-bis(chloromethyoxy)butane which is un-carcinogenic, and grafting particles CMPS/SiO 2 was gained. Subsequently, grafted CMPS was quaternized (denoted as QPS) using tertiary amine, and finally functional composite-type particles QPS/SiO 2, on which quaternary ammonium groups were immobilized, were prepared. The catalysis activity of the particle QPS/SiO 2 as a triphase catalyst in phase-transfer catalysis systems and its antibacterial activity as a water-insoluble antibacterial material were studied preliminarily. The experimental results show that the particle QPS/SiO 2 exhibits higher catalysis activity as a triphase catalyst for the reaction between benzyl chloride in organic phase and sodium acetate in aqueous phase to form benzyl acetate, and under a mild condition of 60 °C for 7 h of reaction time a conversion of 66% for benzyl chloride can be obtained. The particle QPS/SiO 2 has high antibacterial activity as a water-insoluble antibacterial material against Escherichia coli ( E. coli).

  19. Preparation of thermo-responsive polymer brushes on hydrophilic polymeric beads by surface-initiated atom transfer radical polymerization for a highly resolutive separation of peptides.

    PubMed

    Mizutani, Aya; Nagase, Kenichi; Kikuchi, Akihiko; Kanazawa, Hideko; Akiyama, Yoshikatsu; Kobayashi, Jun; Annaka, Masahiko; Okano, Teruo

    2010-09-17

    Poly(N-isopropylacrylamide-co-N-tert-butylacrylamide) [P(IPAAm-co-tBAAm)] brushes were prepared on poly(hydroxy methacrylate) (PHMA) [hydrolyzed poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate)] beads having large pores by surface-initiated atom transfer radical polymerization (ATRP) and applied to the stationary phases of thermo-responsive chromatography. Optimized amount of copolymer brushes grafted PHMA beads were able to separate peptides and proteins with narrow peaks and a high resolution. The beads were found to have a specific surface area of 43.0 m(2)/g by nitrogen gas adsorption method. Copolymer brush of P(IPAAm-co-tBAAm) grafted PHMA beads improved the stationary phase of thermo-responsive chromatography for the all-aqueous separation of peptides and proteins. PMID:20723903

  20. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, J.E.; Herzog, T.A.

    1998-01-13

    A metallocene catalyst system is described for the polymerization of {alpha}-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula shown wherein: R{sup 1}, R{sup 2}, and R{sup 3} are independently selected from the group consisting of hydrogen, C{sub 1} to C{sub 10} alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C{sub 1} to C{sub 10} alkyls as a substituent, C{sub 6} to C{sub 15} aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R{sup 8}){sub 3} where R{sup 8} is selected from the group consisting of C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; R{sup 4} and R{sup 6} are substituents both having van der Waals radii larger than the van der Waals radii of groups R{sup 1} and R{sup 3}; R{sup 5} is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E{sup 1}, E{sup 2} are independently selected from the group consisting of Si(R{sup 9}){sub 2}, Si(R{sup 9}){sub 2}--Si(R{sup 9}){sub 2}, Ge(R{sup 9}){sub 2}, Sn(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}--C(R{sup 9}){sub 2}, where R{sup 9} is C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; and the ligand may have C{sub S} or C{sub 1}-symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from {alpha}-olefin monomers.

  1. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, John E.; Herzog, Timothy A.

    1998-01-01

    A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

  2. One step ATRP initiator immobilization on surfaces leading to gradient-grafted polymer brushes.

    PubMed

    Coad, Bryan R; Styan, Katie E; Meagher, Laurence

    2014-05-28

    A method is described that allows potentially any surface to be functionalized covalently with atom transfer radical polymerization (ATRP) initiators derived from ethyl-2-bromoisobutyrl bromide in a single step. In addition, the initiator surface density was variable and tunable such that the thickness of polymer chain grafted from the surface varied greatly on the surfaces providing examples, across the surface of a substrate, of increased chain stretching due to the entropic nature of crowded polymer chains leading toward polymer brushes. An initiator gradient of increasing surface density was deposited by plasma copolymerization of an ATRP initiator (ethyl 2-bromoisobutyrate) and a non-ATRP reactive diluent molecule (ethanol). The deposited plasma polymer retained its chemical ability to surface-initiate polymerization reactions as exemplified by N,N'-dimethyl acrylamide and poly(ethylene glycol) methyl ether methacrylate polymerizations, illustrating linear and bottle-brush-like chains, respectively. A large variation in graft thickness was observed from the low to high chain-density side suggesting that chains were forced to stretch away from the surface interface--a consequence of entropic effects resulting from increased surface crowding. The tert-butyl bromide group of ethyl 2-bromoisobutyrate is a commonly used initiator in ATRP, so a method for covalent linkage to any substrate in a single step desirably simplifies the multistep surface activation procedures currently used. PMID:24783968

  3. Self-Assembled Polymeric Micelles Based on Hyaluronic Acid-g-Poly(d,l-lactide-co-glycolide) Copolymer for Tumor Targeting

    PubMed Central

    Son, Gyung Mo; Kim, Hyun Yul; Ryu, Je Ho; Chu, Chong Woo; Kang, Dae Hwan; Park, Su Bum; Jeong, Young-IL

    2014-01-01

    Graft copolymer composed hyaluronic acid (HA) and poly(d,l-lactide-co-glycolide) (PLGA) (HAgLG) was synthesized for antitumor targeting via CD44 receptor of tumor cells. The carboxylic end of PLGA was conjugated with hexamethylenediamine (HMDA) to have amine end group in the end of chain (PLGA-amine). PLGA-amine was coupled with carboxylic acid of HA. Self-assembled polymeric micelles of HAgLG have spherical morphologies and their sizes were around 50–200 nm. Doxorubicin (DOX)-incorporated polymeric micelles were prepared by dialysis procedure. DOX was released over 4 days and its release rate was accelerated by the tumoric enzyme hyaluronidase. To assess targetability of polymeric micelles, CD44-positive HepG2 cells were employed treated with fluorescein isothiocyanate (FITC)-labeled polymeric micelles. HepG2 cells strongly expressed green fluorescence at the cell membrane and cytosol. However, internalization of polymeric micelles were significantly decreased when free HA was pretreated to block the CD44 receptor. Furthermore, the CD44-specific anticancer activity of HAgLG polymeric micelles was confirmed using CD44-negative CT26 cells and CD44-positive HepG2 cells. These results indicated that polymeric micelles of HaLG polymeric micelles have targetability against CD44 receptor of tumor cells. We suggest HAgLG polymeric micelles as a promising candidate for specific drug targeting. PMID:25216338

  4. Endovascular Stent-Graft Repair as a Late Secondary Procedure After Previous Aortic Grafts

    SciTech Connect

    Matsagas, Miltiadis I. Anagnostopoulos, Constantine E.; Papakostas, John C.; DeRose, Joseph J.; Siminelakis, Stavros; Katsouras, Christos S.; Toumpoulis, Ioannis K.; Drossos, George E.; Michalis, Lampros K.

    2006-08-15

    Thoracic and abdominal aortic endovascular procedures as alternatives to aortic reoperations were studied in three different cases. An anastomotic aneurysm after previous thoracic aortic graft for coarctation, a second-stage elephant trunk repair (descending thoracic aortic aneurysm), and a secondary aneurysm proximal to a previous abdominal aortic graft were successfully treated with endovascular stent-grafts. During the follow-up period no lethal events or major aortic or graft-related complications were observed, except a type II endoleak in the anastomotic aortic aneurysm case. An endovascular stent-graft can be safely deployed into a previously implanted vascular graft, avoiding repeat surgery.

  5. Facile preparation route for nanostructured composites: surface-initiated ring-opening polymerization of ε-caprolactone from high-surface-area nanopaper.

    PubMed

    Boujemaoui, Assya; Carlsson, Linn; Malmström, Eva; Lahcini, Mohammed; Berglund, Lars; Sehaqui, Houssine; Carlmark, Anna

    2012-06-27

    In this work, highly porous nanopaper, i.e., sheets of papers made from non-aggregated nanofibrillated cellulose (NFC), have been surface-grafted with poly(ε-caprolactone) (PCL) by surface-initiated ring-opening polymerization (SI-ROP). The nanopaper has exceptionally high surface area (∼300 m(2)/g). The "grafting from" of the nanopapers was compared to "grafting from" of cellulose in the form of filter paper, and in both cases either titanium n-butoxide (Ti(On-Bu)4) or tin octoate (Sn(Oct)2) was utilized as a catalyst. It was found that a high surface area leads to significantly higher amount of grafted PCL in the substrates when Sn(Oct)2 was utilized as a catalyst. Up to 79 wt % PCL was successfully grafted onto the nanopapers as compared to filter paper where only 2-3 wt % PCL was grafted. However, utilizing Ti(On-Bu)4 this effect was not seen and the grafted amount was essentially similar, irrespectively of surface area. The mechanical properties of the grafted nanopaper proved to be superior to those of pure PCL films, especially at elevated temperatures. The present bottom-up preparation route of NFC-based composites allows high NFC content and provides excellent nanostructural control. This is an important advantage compared with some existing preparation routes where dispersion of the filler in the matrix is challenging. PMID:22646162

  6. Surface modification of biomaterials by pulsed laser ablation deposition and plasma/gamma polymerization

    NASA Astrophysics Data System (ADS)

    Rau, Kaustubh R.

    Surface modification of stainless-steel was carried out by two different methods: pulsed laser ablation deposition (PLAD) and a combined plasma/gamma process. A potential application was the surface modification of endovascular stents, to enhance biocompatibility. The pulsed laser ablation deposition process, had not been previously reported for modifying stents and represented a unique and potentially important method for surface modification of biomaterials. Polydimethylsiloxane (PDMS) elatomer was studied using the PLAD technique. Cross- linked PDMS was deemed important because of its general use for biomedical implants and devices as well as in other fields. Furthermore, PDMS deposition using PLAD had not been previously studied and any information gained on its ablation characteristics could be important scientifically and technologically. The studies reported here showed that the deposited silicone film properties had a dependence on the laser energy density incident on the target. Smooth, hydrophobic, silicone-like films were deposited at low energy densities (100-150 mJ/cm2). At high energy densities (>200 mJ/cm2), the films had an higher oxygen content than PDMS, were hydrophilic and tended to show a more particulate morphology. It was also determined that (1)the deposited films were stable and extremely adherent to the substrate, (2)silicone deposition exhibited an `incubation effect' which led to the film properties changing with laser pulse number and (3)films deposited under high vacuum were similar to films deposited at low vacuum levels. The mechanical properties of the PLAD films were determined by nanomechanical measurements which are based on the Atomic Force Microscope (AFM). From these measurements, it was possible to determine the modulus of the films and also study their scratch resistance. Such measurement techniques represent a significant advance over current state-of-the-art thin film characterization methods. An empirical model for ablation was developed for the 248 nm laser irradiation of silicone. The model demonstrated a good fit to the experimental data and showed that silicone underwent ablation by a thermal mechanism. In addition to PLAD studies, functionalization of stainless steel was carried out by a combined plasma/gamma method involving deposition of a hexane plasma polymer by RF plasma polymerization, followed by gamma radiation graft polymerization of methacrylic acid. The hydrograft modified surfaces were further modified by chemisorption reactions with poly(ethylene imine) to produce amine-rich surfaces. Bovine serum albumin was then bound via amino groups using glutaraldehyde coupling. A streaming potential cell was also built and used to measure the zeta potential of these ionic surfaces.

  7. The Conchal Cartilage Butterfly Graft.

    PubMed

    Friedman, Oren; Coblens, Orly

    2016-02-01

    Nasal obstruction due to weakening of the nasal sidewall is a very common patient complaint. The conchal cartilage butterfly graft is a proven technique for the correction of nasal valve collapse. It allows for excellent functional results, and with experience and attention to technical detail, it may also provide excellent cosmetic results. While this procedure is most useful for restoring form and function in cases of secondary rhinoplasty following the reduction of nasal support structures, we have found it to be a very powerful and satisfying technique in primary rhinoplasty as well. This article aims to describe the butterfly graft, discuss its history, and detail the technical considerations which we have found useful. PMID:26862963

  8. Temperature-dependent conformational changes of PNIPAM grafted chains in water : effects of molecular weight and grafting density.

    SciTech Connect

    Satija, Sushil K.; Mendez, Sergio; Kent, Michael Stuart; Yim, Hyun; Lopez, Gabriel P.

    2005-03-01

    Poly(N-isopropyl acrylamide) (PNIPAM) is perhaps the most well known member of the class of responsive polymers. Free PNIPAM chains have a lower critical solution temperature in water at {approx}31 C. This very sharp transition ({approx}5 C) is attributed to alterations in the hydrogen bonding interactions of the amide group. Grafted chains of PNIPAM have shown promise for creating responsive surfaces. Examples include controlling the adsorption of proteins or bacteria, regulating the flow of liquids in narrow filaments or mesoporous materials, control of enzymatic activity, and releasing the contents of liposomes. Conformational changes of the polymer are likely to play a role in some of these applications, in addition to changes in local interactions. In this work we investigated the T-dependent conformational changes of grafted PNIPAM chains in D2O using neutron reflection and AFM. The molecular weight (M) and surface density of the PNIPAM brushes were controlled using atom-transfer radical polymerization. We discovered a strong effect of surface density. At lower surface densities, in the range typically achieved with grafting-to methods, we observed very little conformational change. At higher surface densities, significant changes with T were observed. The results will be compared with numerical SCF calculations employing an effective (conc.-dependent) Flory-Huggins chi parameter extracted from the solution phase diagram. For the case of high M and high surface density, a non-monotonic change in profile shape with T was observed. This will be discussed in the context of vertical phase separation predicted for brushes of water-soluble polymers within two-state models.

  9. Space environmental effects on polymeric materials

    NASA Technical Reports Server (NTRS)

    Kiefer, Richard L.; Orwoll, Robert A.

    1987-01-01

    Polymeric materials that may be exposed on spacecraft to the hostile environment beyond Earth's atmosphere were subjected to atomic oxygen, electron bombardment, and ultraviolet radiation in terrestrial experiments. Evidence is presented for the utility of an inexpensive asher for determining the relative susceptibility of organic polymers to atomic oxygen. Kapton, Ultem, P1700 polysulfone, and m-CBB/BIS-A (a specially formulated polymer prepared at NASA Langley) all eroded at high rates, just as was observed in shuttle experiments. Films of Ultem, P1700 polysulfone, and m-CBB/BIS-A were irradiated with 85 keV electrons. The UV/VIS absorbance of Ultem was found to decay with time after irradiation, indicating free radical decay. The tensile properties of Ultem began to change only after it had been exposed to 100 Mrads. The effects of dose rate, temperature, and simultaneous vs. sequential electron and UV irradiation were also studied.

  10. Hybrid Graft Anterior Cruciate Ligament Reconstruction: A Predictable Graft for Knee Stabilization.

    PubMed

    Alvarez-Pinzon, Andres M; Barksdale, Leticia; Krill, Michael K; Leo, Brian M

    2015-06-01

    Trauma to the anterior cruciate ligament (ACL) is a season-ending injury and involves months of activity modification and rehabilitation. The annual incidence of ACL tears in the United States is approximately 200,000, which allows for a broad range of individualized treatment options. Various surgical techniques, including transtibial and independent tunnel drilling, allograft and autograft tissue, and various implants, have been described in the literature. This article describes the indications and technique for a hybrid soft tissue graft for ACL reconstruction. Autologous grafts eliminate the risk of disease transmission and have recently been shown to have a lower rerupture rate, particularly in younger, active patients; however, the harvesting of autologous hamstring grafts carries a risk of donor-site morbidity, iatrogenic injury of the graft, and inadequate graft size. In contrast to a traditional autologous soft tissue graft, the hybrid graft allows for graft size customization for a desired reconstruction, especially in cases where autograft hamstrings may be iatrogenically damaged or of inadequate size when harvested. The goal of a hybrid graft ACL reconstruction is to provide a favorable-sized graft with clinical outcomes comparable with autologous soft tissue grafts. In contrast to a traditional autologous soft tissue graft, this technique provides another option in the event of unforeseen deficiencies or complications associated with harvesting and preparation of the autologous gracilis and semitendinosis soft tissue graft. PMID:26091219

  11. On-demand photoinitiated polymerization

    DOEpatents

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2013-12-10

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  12. On-demand photoinitiated polymerization

    SciTech Connect

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2015-01-13

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  13. Characterization of poly(Sodium Styrene Sulfonate) Thin Films Grafted from Functionalized Titanium Surfaces

    PubMed Central

    Zorn, Gilad; Baio, Joe E.; Weidner, Tobias; Migonney, Veronique; Castner, David G.

    2011-01-01

    Biointegration of titanium implants in the body is controlled by their surface properties. Improving surface properties by coating with a bioactive polymer is a promising approach to improve the biological performance of titanium implants. To optimize the grafting processes, it is important to fully understand the composition and structure of the modified surfaces. The main focus of this study is to provide a detailed, multi-technique characterization of a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film grafted from titanium surfaces via a two-step procedure. Thin titanium films (~50 nm thick with an average surface roughness of 0.9±0.2nm) prepared by evaporation onto silicon wafers were used as smooth model substrates. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that the titanium film was covered with a TiO2 layer that was at least 10nm thick and contained hydroxyl groups present at the outermost surface. These hydroxyl groups were first modified with a 3-methacryloxypropyltrimethoxysilane (MPS) cross linker. XPS and ToF-SIMS showed that a monolayer of the MPS molecules were successfully attached onto the titanium surfaces. The pNaSS film was grafted from the MPS modified titanium through atom transfer radical polymerization. Again, XPS and ToF-SIMS were used to verify that the pNaSS molecules were successfully grafted onto the modified surfaces. Atomic force microscopy analysis showed that the film was smooth and uniformly covered the surface. Fourier transform infrared spectroscopy indicated an ordered array of grafted NaSS molecules were present on the titanium surfaces. Sum frequency generation vibration spectroscopy and near edge X-ray absorption fine structure spectroscopy illustrated that the NaSS molecules were grafted onto the titanium surface with a substantial degree of orientational order in the styrene rings. PMID:21892821

  14. Universal Surface-initiated Polymerization of Antifouling Zwitterionic Brushes Using A Mussel-Mimetic Peptide Initiator

    PubMed Central

    Kuang, Jinghao; Messersmith, Phillip B.

    2012-01-01

    We report a universal method for the surface-initated polymerization (SIP) of a antifouling polymer brush on various classes of surfaces, including noble metals, metal oxides and inert polymers. Inspired by the versatility of mussel adhesive proteins, we synthesized a novel bifunctional tripeptide bromide (BrYKY) which combines an atom transfer radical polymerization (ATRP) initiating alkyl bromide with l-3,4-dihydroxyphenylalanine (DOPA) and lysine. Simple dip-coating of substrates with variable wetting properties and compositions, including Teflon®, in a BrYKY solution at pH 8.5 led to formation of a thin film of cross-linked BrYKY. Subsequently, we showed that the BrYKY layer initiated the ATRP of a zwitterionic monomer, sulfobetaine methacrylate (SBMA) on all substrates, resulting in high density antifouling pSBMA brushes. Both BrYKY deposition and pSBMA grafting were unambiguously confirmed by ellipsometry, X-ray photoelectron spectroscopy and goniometry. All substrates that were coated with BrYKY/pSBMA dramatically reduced bacterial adhesion for 24 h and also resisted mammalian cell adhesion for at least 4 months, demonstrating the long-term stability of the BrYKY anchoring and antifouling properties of pSBMA. The use of BrYKY as a primer and polymerization initiator has the potential to be widely employed in surface grafted polymer brush modifications for biomedical and other applications. PMID:22506651

  15. Surface modification by γ-ray-induced grafting of PDMAEMA/PEGMEMA onto PE films

    NASA Astrophysics Data System (ADS)

    Titaux, G. A.; Contreras-García, A.; Bucio, E.

    2009-07-01

    Radiation grafting of poly[2-(dimethylamino) ethyl methacrylate] (PDMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) onto polyethylene (PE) films was synthesized using gamma radiation from a 60Co source. PE was modified by the PDMAEMA and PEGMEMA by pre-irradiation and one-step method. Grafting as a function of the pre-irradiation dose between 50 and 200 kGy, dose rate of 9 kGy h -1, and monomer concentration 50% of PDMAEMA/PEGMEMA (1/1) in toluene. The characterization of the graft copolymer obtained was carried out by FTIR-ATR, TGA, and DSC. Stimuli-responsive behavior and critical pH point were studied by swelling in water, pH and thermo-responsive films of PE-g-(DMAEMA/PEGMEMA) presented a lower critical solution temperature (LCST) of 55 °C and critical pH point around 8.5.

  16. UV-Induced [2+2] Grafting-To Reactions for Polymer Modification of Cellulose.

    PubMed

    Conradi, Matthias; Ramakers, Gijs; Junkers, Thomas

    2016-01-01

    Benzaldehyde-functional cellulose paper sheets have been synthesized via tosylation of cellulose (Whatman No 5) followed by addition of p-hydroxy benzaldehyde. Via UV-induced Paterno-Büchi [2+2] cycloaddition reactions, these aldehyde functional surfaces are grafted with triallylcyanurate, trimethylolpropane allyl ether, and vinyl chloroacetate. In the following, allyl-functional polymers (poly(butyl acrylate), pBA, Mn = 6990 g mol(-1) , Đ = 1.12 and poly(N-isopropyl acrylamide), pNIPAAm, Mn = 9500 g mol(-1) , Đ = 1.16) synthesized via reversible addition fragmentation chain transfer polymerization are conjugated to the celloluse surface in a UV-induced grafting-to approach. With pBA, hydrophobic cellulose sheets are obtained (water contact angle 116°), while grafting of pNIPAAm allows for generation of "smart" surfaces, which are hydrophilic at room temperature, but that become hydrophobic when heated above the characteristic lower critical solution temperature (93° contact angle). The Paterno-Büchi reaction has been shown to be a versatile synthetic tool that also performs well in grafting-to approaches whereby its overall performance seems to be close to that of radical thiol-ene reactions. PMID:26523942

  17. High Surface Area Poly(3-hexylthiophenes) Thin Films from Cleavable Graft Copolymers

    SciTech Connect

    Sivanandan, Kulandaivelu; Chatterjee, Tirtha; Treat, Neil; Kramer, Edward J.; Hawker, Craig J.

    2010-03-30

    A strategy for the fabrication of high surface area poly(3-hexylthiophene) thin films by removal of nanoscale domains formed from graft copolymers is presented. This approach relies on the synthesis and characterization of cleavable graft copolymers based on regioregular poly(3-hexylthiophene) (rr-P3HT) main chain and sacrificial poly(styrene) side chains. An alkoxyamine initiator based on 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) was incorporated at the 3-position of the functionalized thienyl repeat unit, 2, via a cleavable trityl ether linker. Grignard metathesis (GRIM) copolymerization of 2 and 2,5-dibromo-3-hexylthiophene afforded regioregular P3HT with randomly incorporated alkoxyamine groups. Polymerization of styrene from the P3HT backbone for different time periods afforded graft copolymers with controllable sacrificial chain lengths. These materials were characterized using an array of techniques such as {sup 1}H and {sup 13}C NMR spectroscopy and size exclusion chromatography (SEC). An approach to obtain nanoporous P3HT thin films by cleavage of the trityl ether linker followed by complete removal of poly(styrene) is reported with the as-cast graft copolymer thin films displaying an irregular microphase-separated structure with an average domain size {approx}30 nm as determined by grazing incidence small-angle X-ray scattering (GISAXS) measurements. Significantly, this length scale was conserved after removal of the sacrificial component which allows this strategy to have potential application in diverse fields such as organic photovoltaics.

  18. Controlled mechanical and swelling properties of urethane acrylate grafted calcium alginate hydrogels.

    PubMed

    Wang, Jichao; Ying, Xiaoguang; Liu, Jiangquan; Li, Xiao; Zhang, Weiying

    2015-11-01

    Vinyl group capped urethane acrylate (UA) was prepared with diisocyanate (IPDI), hydroxyethyl methacrylate (HEMA) and dimethylolpropionic acid (DMPA). The UA was grafted onto sodium alginate via free-radical polymerization with KPS/Na2SO3 as initiator and then crosslinked by Ca(2+). Grafted polymers (UA-g-CaA) were characterized by FT-IR, SEM, TGA, XRD and tension gauge. The swelling behavior was also investigated. It is found that urethane acrylate grafted calcium alginate possesses lower swelling degree and is improved in thermal stability as well as mechanical performance. The reason is that hydrophobic urethane acrylate provides alginate with physical crosslinking and forms partial crystal regions. The optimum condition for synthesis of UA-g-CaA with lower swelling degree is that weight percentage of initiator to monomer is 0.8%, mass ratio of reductant to oxidant is 0.45:1, monomer concentration is 0.0385mol/L and grafting reaction temperature is 55°C. PMID:26188298

  19. Extraction of palm tree cellulose and its functionalization via graft copolymerization.

    PubMed

    Al-Hoqbani, Abdulmajeed A; Abdel-Halim, E S; Al-Deyab, Salem S

    2014-09-01

    The work in this paper was planned with the aim of extracting the cellulosic component of palm tree waste and functionalizing this cellulose through graft copolymerization with acrylic acid. The cellulose extraction included hot alkali treatment with aqueous sodium hydroxide to remove the non-cellulosic binding materials. The alkali treatment was followed by an oxidative bleaching using peracid/hydrogen peroxide mixture with the aim of removing the rest of non-cellulosic materials to improve the fiber hydrophilicity and accessibility towards further grafting reaction. Optimum conditions for cellulose extraction are boiling in 5% (W/V) NaOH in a material to liquor ratio of 1:20 for 1 h then bleaching with 60 ml/l bleaching mixture at initial pH value of 6.5 for 30 min. The pH of the bleaching medium is turned to the alkaline range 11 and bleaching continues for extra 30 min. Graft copolymerization reaction was initiated by potassium bromate/thiourea dioxide redox system. Optimum conditions for grafting are 30 mmol of potassium bromate, 30 mmol of thiourea dioxide and 150 g of acrylic acid (each per 100 g of cellulose). The polymerization reaction was carried out for 120 min at 50°C using a material to liquor ratio of 1:20. PMID:25020080

  20. Tensile Properties of Polyimide Composites Incorporating Carbon Nanotubes-Grafted and Polyimide-Coated Carbon Fibers

    NASA Astrophysics Data System (ADS)

    Naito, Kimiyoshi

    2014-09-01

    The tensile properties and fracture behavior of polyimide composite bundles incorporating carbon nanotubes-grafted (CNT-grafted) and polyimide-coated (PI-coated) high-tensile-strength polyacrylonitrile (PAN)-based (T1000GB), and high-modulus pitch-based (K13D) carbon fibers were investigated. The CNT were grown on the surface of the carbon fibers by chemical vapor deposition. The pyromellitic dianhydride/4,4'-oxydianiline PI nanolayer coating was deposited on the surface of the carbon fiber by high-temperature vapor deposition polymerization. The results clearly demonstrate that CNT grafting and PI coating were effective for improving the Weibull modulus of T1000GB PAN-based and K13D pitch-based carbon fiber bundle composites. In addition, the average tensile strength of the PI-coated T1000GB carbon fiber bundle composites was also higher than that of the as-received carbon fiber bundle composites, while the average tensile strength of the CNT-grafted T1000GB, K13D, and the PI-coated K13D carbon fiber bundle composites was similar to that of the as-received carbon fiber bundle composites.